Traditionally, fossil fuels have served as a primary energy source for much of the world's energy needs. However, fossil fuels are undesirable because their use results in substantial pollution being released into the environment. As such, alternative fuel sources that release less pollution into the environment are generally desirable.
One fuel source being investigated as an alternative to fossil fuels is hydrogen, because hydrogen can be safely transported converted to usable energy with little or no pollution being released into the environment, as the primary by-product is of hydrogen fuel cell operation is liquid water. One significant impediment to adoption of hydrogen as a fuel source is that the creation of hydrogen requires substantial energy and therefore cost.
One way to generate hydrogen is to split liquid water, an abundant resource on our planet, into hydrogen and oxygen. Since sunlight is an unlimited resource on our planet, some have attempted to develop photoelectrochemical (PEC) cells designed to collect energy from incident sunlight, and use the collected energy to separate water molecules into oxygen and hydrogen useable as a fuel. While some success has been found developing PEC cells, they suffer from significant drawbacks, such as low efficiency and short longevity. As such, a need exists to provide improvements in PEC cells for water splitting.
According to one aspect of the disclosure, a photoelectrochemical (PEC) water splitting cell is comprised of a semiconductor layer and an electrode layer arranged at a second surface of the semiconductor layer. The semiconductor layer comprises a light capture surface arranged at a first side, wherein the semiconductor layer comprises a buried junction configured to convert incident electromagnetic energy into electrical energy. The electrode layer includes an anode electrode configured to catalyze hydrogen, and a cathode electrode configured to catalyze oxygen.
According to another aspect, a method of forming a photoelectrochemical cell includes patterning a first side of a semiconductor substrate. The method further includes doping a second side of the semiconductor substrate to form a buried junction layer, wherein the buried junction layer comprises a first plurality of doped regions and a second plurality of doped regions arranged in an alternating pattern and forming an electrode layer at the second side of the semiconductor substrate, wherein the electrode layer includes an anode electrode comprising a first plurality of fingers arranged in an interdigitated alternating pattern with a cathode electrode comprising a second plurality of fingers.
According to another aspect of the disclosure, a method includes receiving, at a first side of a photoelectrochemical (PEC) cell, electromagnetic energy. The method further includes converting, via a buried junction of the PEC cell, the received electromagnetic energy into electrical energy and using, at an anode electrode and a cathode electrode arranged at a second side of the PEC cell, the converted electrical energy to catalyze water into hydrogen and oxygen.
This disclosure is directed to devices, methods, and techniques providing for improvements in water splitting to generate hydrogen which may be used for numerous applications, including as a “clean” (low emissions) energy source.
A potential solution for storing converted solar energy would be to directly store solar energy in the hydrogen gas fuels or hydrocarbons that combine the advantages of large scale storage, transported, combusted, or ultimately consumed on demand using a fuel cell device to generate electricity. The solar-drive PEC water splitting consists of three fundamental steps to generate hydrogen: (i) charge carrier generation via photo-excitation, (ii) separation/transportation of charge carriers to the surfaces, and (iii) the utilization of photo-excited carriers to drive catalytic water reduction or oxidation at the surfaces.5 As the most investigated photoelectrode, Si, high-performing photon absorber with optimal bandgap (Eg=1.1 eV) has 2 dilemmas avoiding efficient solar-to-hydrogen conversion: (i) the poor kinetics without the electrocatalyst for splitting water and (ii) the small bandgap which can not straddle both reduction (0.0 VRHE) and oxidation (1.23 VRHE) potentials of water. To work around the spontaneous solar-dive hydrogen evolution constraint, the most practical and cost-effective ways for achieving efficient solar-to-hydrogen conversion is by employing an integrated PEC device configuration as described herein, in which one integrated PEC device may be coupled in series with other integrated PEC device to provide an additional voltage to a single bandgap water-splitting device for driving the hydrogen/oxygen evolution reactions. herein
For example, a photoelectrochemical (PEC) cell is described herein. The PEC cell includes a semiconductor layer comprising a light capture surface arranged at a first side. The semiconductor layer comprises a buried junction configured to convert incident electromagnetic energy into electrical energy. The PEC cell further includes an electrode layer arranged at a second surface of the semiconductor layer that includes an anode electrode configured to catalyze hydrogen, and a cathode electrode configured to catalyze oxygen.
As another example, a method of forming a photoelectrochemical cell is described herein. The method includes patterning a first side of a semiconductor substrate. The method further includes doping a second side of the semiconductor substrate to form a buried junction layer, wherein the buried junction layer comprises a first plurality of doped regions and a second plurality of doped regions arranged in an alternating pattern. The method further includes forming an electrode layer at the second side of the semiconductor substrate, wherein the electrode layer includes an anode electrode comprising a first plurality of fingers arranged in an interdigitated alternating pattern with a cathode electrode comprising a second plurality of fingers.
As another example, a method is described herein. The method includes receiving, at a first side of a photoelectrochemical (PEC) cell, electromagnetic energy. The method further includes converting, via a buried junction of the PEC cell, the received electromagnetic energy into electrical energy. The method further includes using, at an anode electrode and a cathode electrode arranged at a second side of the PEC cell, the converted electrical energy to catalyze water into hydrogen and oxygen.
Attempts have been made to use readily available electromagnetic energy, such as sunlight, to split water to generate hydrogen. For example, photoelectrochemical (PEC) cells have been developed that are capable of using sunlight to split water molecules for purposes of creating hydrogen. Such PEC cells utilize a photo-sensitive semiconductor to convert electromagnetic energy (e.g., sunlight) into electrical energy which, when submerged in an electrolyte solution (e.g., liquid water) powers catalysis of water molecules into oxygen and hydrogen at respective anode and cathode electrodes of the cell.
In a PEC cell, incident sunlight excites free electron-hole pairs in the cell. These electron-hole pairs are separated at buried p-n junction, which the electrons flow to a cathode electrode (n+-Si) and the holes flow to a anode electrode (p+-Si). At the cathode electrode, four electrons react with four water molecules to form two molecules of hydrogen and four OH− groups (4H2O(1)+4e−→2H2(g)+4OH−(aq)). The OH− groups flow through the liquid electrolyte to the surface of the anode electrode. At the anode electrode, the four OH− groups react with the four holes, the result being two water molecules and an oxygen molecule (4OH−(aq)+4h+→O2(g)+2H2O(1)). The anode electrode may be described as configured to catalyze oxygen, while the cathode electrode may be described as configured to catalyze hydrogen.
A typical PEC cell as described above includes a non-transparent metal-based electrode (anode) arranged at a light receiving surface of the PEC. Such a typical PEC cell may also include only a single photo-sensitive p-n junction arranged in parallel to the light receiving surface of the cell.
A typical PEC cell may suffer from significant drawbacks in efficiency and longevity. For example, such a PEC cell may suffer from “shadow effects” in that non-transparent metallization (e.g., finger electrodes) block a portion of the exposed surface of the photosensitive semiconductor material, and therefore reduce the PEC cell's ability to convert received light into electrical energy. In addition, overloading or aggregation of cocatalysts may reduce the ability of a photosensitive semiconductor material to convert incident light into electrical energy, thereby reducing the efficiency of the cell to split water molecules.
This disclosure is directed to improvements in PEC cells used to split water molecules. According to some aspects, a PEC cell does not include any electrodes on the surface of the photosensitive semiconductor material configured to be exposed to light (light capture surface). Instead, both a cathode electrode and an anode electrode are arranged on a same side of the PEC cell. According to these aspects, both the anode and cathode electrodes are arranged on a side of the PEC cell opposed to a light capture surface of the cell.
According to still other aspects, a PEC cell includes one or more buried p-n junctions in the photosensitive semiconductor material. The buried junction may be arranged substantially perpendicular to the light capture surface of the semiconductor material (hereinafter referred to as a “vertical junction”), in contrast with typical PEC cell designs which include a junction arranged in parallel to the light capture surface of the PEC cell (hereinafter referred to as a “horizontal junction”). According to still other aspects, a PEC cell is described herein that includes a plurality of p-n junctions that are each vertical junctions arranged substantially in parallel to the light capture surface of the PEC cell.
According to still other aspects of this disclosure, an anode and cathode electrode of the PEC cell are arranged proximal to the buried p-n junctions of the cell, which substantially shortens the electrical path for charge carriers to travel, leading to improved operational efficiency of the PEC cell.
According to still other aspects, a light capture surface of a PEC cell as described herein is processed to be protected when submerged in a liquid electrolyte solution, and to improve light capture properties of the PEC cell. For example, a light capture surface of the photosensitive semiconductor material may be lightly doped in order to improve an ability to reflect charge carriers towards a buried junction of the PEC cell. As another example, the light capture surface of the semiconductor material is patterned to form a plurality of micropyramid structures to improve the light capture capability of PEC cell. As still another example, an insulator layer, such as silicon dioxide, is formed upon the light capture surface of the semiconductor layer to protect the photosensitive semiconductor from a solution when submerged. In still other examples, the insulator layer is also formed to include a plurality of micropyramid structures.
A PEC cell as described herein may provide significant benefits in comparison to other PEC cells. For example, the PEC cell described herein may exhibit superior light-harvesting capability over 95% in the wide range of solar spectrum from 300 to 1100 nm As another example, a single PEC cell as described herein may achieve a current density of 41.76 mA/cm2 for hydrogen evolution with an open-circuit potential of 0.62 V and a solar-to-hydrogen conversion efficiency (SHCE) of 11.44%. In some examples, a plurality of PEC cells may be coupled together to improve functionality. For example, three of the PEC cells described herein may be coupled in series and perform unassisted water splitting, with an SHCE of 15.62% with 240 μg.cm−2h−1 of hydrogen. As another example, a PEC cell as described herein may provide for improved longevity when in operation submerged in an electrolyte solution such as liquid water, for example a PEC cell of this disclosure may operate for 40 hours or more.
As shown in
Semiconductor layer 101 is substantially formed of a semiconductor material, such as crystalline silicon. As depicted in
First portion 121 is doped with material elements that cause first portion 121 to exhibit p-type semiconductor characteristics. For example, the first portion 121 may be doped with Boron (Br), or any other element that causes first portion 121 to exhibit P-type characteristics, such as Aluminum (Al) or Gallium (Ga). Second portion 123 is doped with material elements that cause the second portion to exhibit n-type semiconductor characteristics. For example, second portion 123 may be doped with Phosphorous (P), or any other element which causes second portion 109 to exhibit n-type characteristics, for example Antimony (Sb) or Arsenic (As).
As also shown in
Electrode layer 107 includes electrodes 131, 133 each respectively in contact with first and second portions 121, 123 of semiconductor layer 101. In the example of
At least a portion of electrodes 131, 133 respectively comprise materials and or coatings to facilitate the conversion of water atoms into hydrogen and oxygen atoms. For example, anode electrode 131 may be formed of or include one or more coatings that facilitate catalysis of oxygen atoms. As one particular example, at least a portion of electrode 131 includes Nickel (Ni) to facilitate catalysis of hydrogen atoms. At least a portion of cathode electrode 133 may be coated with or otherwise include additional materials that facilitate catalysis of oxygen atoms. As one particular example, electrode 133 may include or be coated with Platinum (Pt) to facilitate catalysis of oxygen atoms.
At least a portion of PEC cell 100 may be submerged in an electrolyte fluid, such as water (H2O). When PEC cell 100 is submerged, and light capture surface 103 is exposed to light, electrical current may flow across buried junction 122, and thereby cause current to flow between anode electrode 131 and cathode electrode 133. When electrical current flows between them, electrodes 131 and 133 each respectively interact with the electrolyte fluid to catalyze hydrogen and oxygen atoms.
For example, sunlight incident on PEC cell 100 may excite free charge carriers (electrons and holes) at buried junction 122. Excited electrons may flow to cathode electrode 133, while exited holes may flow to anode electrode 131. At cathode 133, the four electrons react with four water molecules to form two molecules of hydrogen and four OH− groups (4H2O(1)+4e−2H2(g)+4OH−(aq)). The OH− groups flow through the liquid electrolyte to the surface of the anode electrode 131, wherein the four OH− groups react with four holes, resulting in catalysis of two water molecules and an oxygen molecule (4OH−(aq)+4h+→O2(g)+2H2O(1)).
In this manner, PEC cell 100 functions to split water into hydrogen and oxygen, thereby converting received electromagnetic energy such as sunlight into a hydrogen “fuel.” Such a hydrogen fuel may then be used to power one or more hydrogen fuel cells, which advantageously supply easily transportable power with little or no polluting emissions.
As described above, a typical PEC cell includes an anode electrode at the light capture surface of the cell, and the cathode electrode is arranged elsewhere (e.g., an opposed surface of the cell). According to a such PEC cell, charge carriers travel between a wire connection between the anode electrode and the cathode electrode. In comparison, PEC cell 100 includes both anode and cathode electrodes at a same surface of the cell arranged proximally to buried junction layer 113, thereby enabling a shortened electrical connection between respective portions 121, 123 of buried junction layer 113 to the respective anode and cathode electrodes 131, 133.
As also shown in the example of
In some examples, a light capture surface 103 PEC cell 100 is processed to improve an ability of cell to generate electrical energy from received light. For example, light capture surface 103 may be lightly doped with a P-type semiconductor, such as Boron, which reduces recombination of electrical carriers (holes, electrons) at light capture surface 103. In additional examples, like passivation layer 115, light capture surface 103 is also patterned to include micropyramid structures that improve light capture characteristics of semiconductor layer 101.
PEC cell 100 shown in
According to the example of
Doped first strips 221A-221B are doped with a first doping type, for example p-doped (e.g., Boron doped). Doped second strips 223A-223C are doped with a second doping type different than the first doping type, for example n-doped (e.g., Phosphorous doped). In some examples, doped first strips 221A-221B may be wider than doped second strips 223A-223C, due to hole mobility of the p-doped first strips 221A-221B being less than electron mobility of the n-doped second strips 223A-223C. As a specific non-limiting example, doped first strips 221A-221B have a width of ˜400 μm, while doped second strips 223A-223C have a width of ˜250 μm.
In operation, when exposed to electromagnetic energy such as sunlight, the plurality of vertical buried junctions between first strips 221A-221B and second strips 223A-223C cause excitation of charge carriers (holes, electrons). Excited charge carriers may be transferred to anode electrode 321 and cathode electrode 323, which are configured to interact with an electrolyte solution PEC cell 200 is disposed in, to catalyze oxygen and hydrogen atoms, respectively.
As shown in the example of
As shown in the example of
The example PEC cell 200 depicted in
In addition, the example of
In some examples, anode electrode 321 and cathode electrode 323 are formed of a conductive metal, such as aluminum. In some examples, at least a portion of exposed surfaces of anode electrode 321 and cathode electrode 323 may be coated with one or more materials to facilitate catalysis of hydrogen and oxygen atoms respectively. For example, an exposed surface of anode electrode 321, which is configured to catalyze oxygen, may be coated with or otherwise include Nickel (Ni) to facilitate generation and/or collection of oxygen atoms. As another example, an exposed surface of cathode electrode 323, which is configured to catalyze hydrogen, may be coated with or otherwise include Platinum (P1) to facilitate generate and/or collection of hydrogen atoms.
In the example of
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As also shown in
In some examples, insulating interface layer 205 is coated with an anti-reflective material, to reduce the reflection of light so that more light reaches buried junction layer 213 to be converted to electrical energy. For example, insulating interface layer 205 may be coated with an anti-reflection material such as SiNx, (e.g., silicon nitrate (SiN2) or silicon nitride (SiN3)). In some examples, a bottom surface of buried junction layer 113 may include a conductive material (not shown in
As shown in the example of
In some examples, light capture surface 203 that is treated to improve function of semiconductor layer 201 to generate electrical energy from received light. For example, light capture surface 203 may be lightly doped with a P-type semiconductor, such as Boron, which may reduce recombination of electrical carriers (holes, electrons) at light capture surface 203. In additional examples, like passivation layer 215, light capture surface 203 may also be patterned to include micropyramid structures that improve light capture characteristics of semiconductor layer 201.
Although not depicted in
Although the PEC cell 200 depicted in
The exemplary PEC cell 200 depicted in
PEC cell 200 depicted in
As shown, PEC cell 400 further includes insulating interface layer 405. Insulating interface layer 405 is disposed between buried junction layer 413 and electrode layer 407. Insulating interface layer includes a plurality of apertures configured to receive vertical contacts 450, 460 of electrodes 431, 433 and couple them to doped strips 421, 423, respectively.
As also shown in the example of
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As shown in the example of
As described above with respect to
In still other examples, such as shown in
Each PEC cell 600A-600C includes an anode electrode 621 comprising a plurality of fingers, and a cathode electrode 623 comprising a plurality of fingers arranged in an interdigitated, alternating pattern with the plurality of fingers of the anode electrode 621, at least one P+ contact 670 coupled to the anode electrode 621, and at least one N+ contact 680 coupled to the cathode electrode 623. The P+ contacts 670 serve as a catalyst surface to facilitate catalysis of hydrogen , while the N+ contacts 680 serve as a catalyst surface to facilitate catalysis of oxygen.
In addition, the respective P+ and N+ contacts 670 may provide an electrical contact point, for coupling circuitry to perform measurements, or to electrically couple respective PEC cells 600A-600C to one another. For example, as shown in the
As shown in
Substrate 890 and Protective cover 891 may be formed of quartz or glass, or any other material that protects the respective PEC cells and components while allowing light to reach the light capture surfaces of the respective PEC cells of PEC module 800.
The respective exposed N+ contact 880 and exposed P+ contact 870 comprise the P+ (anode) and N+ cathode electrodes of the PEC module 800. Accordingly P+ contact 870 may be coated with a material to facilitate catalysis of oxygen, such as Nickel, while N+ contact 880 may be coated with a material to facilitate catalysis of hydrogen, such as Platinum.
PEC module 800 depicted in
As shown in
According to some examples not depicted in
As also shown in
In some examples, the one or more P+ regions are a plurality of doped first strips (221A-221B), and the one or more N+ regions are a plurality of doped second strips (223A-223C) formed in an alternating pattern. In some examples, the one or more doped first strips (221A-221B) are wider than the one or more doped second strips (223A-223C). In some examples, the doped first strips (221A-221B) are P-doped strips formed by ion implantation of an element such as Boron (Br). As another example, the doped second strips (223A-223C) are n-doped strips formed by ion implantation with an element such as phosphorus (P).
In some examples, one or more of doped first strips 221A-221B and doped second strips 223A-223C may be additionally processed to form an electrical contact. For example, a Tin (Sn) foil may be soldered onto a bottom surface one or more of doped first and second strips (221A-221B and 223A-223C) to form electrical contacts. In still other examples, different metals may be used to form electrical contacts to doped first and second strips (221A-221B and 223A-223C). For example, Nickel may be formed on doped first strips (221A-221B) to form an electrical contact.
As also shown in
Although not depicted in
The PEC cell (200) may be heated to a temperature of ˜950 degrees C. to activate dopants at first side (204) and second side (206) of the PEC cell in a single step.
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In some examples, not shown in
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The following are non-exclusive descriptions of possible embodiments of the present invention.
A photoelectrochemical (PEC) water splitting cell is comprised of a semiconductor layer and an electrode layer arranged at a second surface of the semiconductor layer. The semiconductor layer comprises a light capture surface arranged at a first side, wherein the semiconductor layer comprises a buried junction configured to convert incident electromagnetic energy into electrical energy. The electrode layer includes an anode electrode configured to catalyze hydrogen, and a cathode electrode configured to catalyze oxygen.
The PEC water splitting cell of the preceding paragraph can optionally include, additionally and/or alternatively any, one or more of the following features. configurations and/or additional components.
The PEC cell may further include wherein when the first and second electrode are in contact with an electrolyte solution comprising water and are supplied with electrical energy from the buried junction, the first and second electrodes catalyze water into hydrogen and oxygen.
The PEC cell may further include wherein the buried junction layer comprises a vertical buried junction layer.
The PEC cell may further include wherein the buried junction layer includes a first plurality of doped regions and a second plurality of doped regions arranged in an alternating pattern.
The PEC cell may further include wherein the buried junction layer includes the first plurality of doped regions comprising a plurality of N-type strips, and the second plurality of doped regions compring a plurality of P-type strips arranged in the alternating pattern.
The PEC cell may further include wherein the anode electrode comprises a first plurality of fingers and the cathode electrode comprises a second plurality of fingers arranged in an interleaved alternating pattern with the first plurality of fingers.
The PEC cell may further include wherein the first plurality of fingers of the anode electrode are sized, shaped, and arranged to align with and electrically connect to a plurality of n-doped strips of the buried junction layer, and the second plurality of fingers of the cathode electrode are sized, shaped, and arranged to align with and electrically connect to a plurality of p-doped strips of the buried junction layer.
The PEC cell may further comprise an insulator layer arranged between the electrode layer and the buried junction layer, wherein the first electrode is electrically connected to the plurality of n-doped strips and the second electrode is electrically connected to the plurality of p-doped strips through the insulator layer.
The PEC cell may further include wherein the buried junction is arranged proximal to and electrically coupled with the electrode layer.
In another embodiment, a method of forming a photoelectrochemical cell. The method includes patterning a first side of a semiconductor substrate. The method further includes doping a second side of the semiconductor substrate to form a buried junction layer, wherein the buried junction layer comprises a first plurality of doped regions and a second plurality of doped regions arranged in an alternating pattern, and forming an electrode layer at the second side of the semiconductor substrate, wherein the electrode layer includes an anode electrode comprising a first plurality of fingers arranged in an interdigitated alternating pattern with a cathode electrode comprising a second plurality of fingers.
The method of the preceding paragraph can optionally include, additionally and/or alternatively any, one or more of the following features, configurations and/or additional components.
The method may further include electrically coupling the first plurality of doped regions to anode electrode and the second plurality of doped regions to the cathode electrode.
The method may further include depositing a passivation layer on the first side of the semiconductor substrate.
In another embodiment, a method includes receiving, at a first side of a photoelectrochemical (PEC) cell, electromagnetic energy. The method further includes converting, via a buried junction of the PEC cell, the received electromagnetic energy into electrical energy and using, at an anode electrode and a cathode electrode arranged at a second side of the PEC cell, the converted electrical energy to catalyze water into hydrogen and oxygen.
The method of the preceding paragraph can optionally include, additionally and/or alternatively any, one or more of the following features, configurations and/or additional components.
The method may further include electrically coupling the first plurality of doped regions to the anode electrode and the second plurality of doped regions to the cathode electrode.
The method may further include depositing a passivation layer on the first side of the semiconductor substrate.
The method may further include receiving, at a first side of a photoelectrochemical (PEC) cell, electromagnetic energy. The method may further include converting, via a buried junction of the PEC cell, the received electromagnetic energy into electrical energy and using, at an anode electrode and a cathode electrode arranged at a second side of the PEC cell, the converted electrical energy to catalyze water into hydrogen and oxygen.
The method may further include submerging at least a portion of the PEC cell in an electrolyte solution, wherein the anode electrode and the cathode electrode interact with the electrolyte solution to catalyze hydrogen and oxygen.
The method may further include wherein the buried junction comprises a vertical buried junction.
The method may further include wherein the buried junction comprises a first plurality of doped regions and a second plurality of doped regions arranged in an alternating pattern.
The method may further include wherein the buried junction layer includes the first plurality of doped regions comprising a plurality of N-type strips, and the second plurality of doped regions comprising a plurality of P-type strips arranged in the alternating pattern.
The method may further include wherein the anode electrode comprises a first plurality of fingers and the cathode electrode comprises a second plurality of fingers arranged in an interleaved alternating pattern with the first plurality of fingers.
The method may further include wherein the first plurality of fingers of the anode electrode are sized, shaped, and arranged to align with and electrically connect to a plurality of n-doped strips of the buried junction layer, and the second plurality of fingers of the cathode electrode are sized, shaped, and arranged to align with and electrically connect to a plurality of p-doped strips of the buried junction layer.
The method may further include wherein the buried junction is arranged proximal o and electrically coupled with the electrode layer.
This application claims the benefit of U.S. Provisional Patent Application No. 62/657,073, filed Apr. 13, 2018, and of U.S. Provisional Patent Application No. 62/659,398, filed Apr. 18, 2018, both of which are incorporated by reference herein in their entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/IB2019/053046 | 4/12/2019 | WO | 00 |
Number | Date | Country | |
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62657073 | Apr 2018 | US | |
62659398 | Apr 2018 | US |