Multi-junction artificial photosynthetic cell with enhanced photovoltages

• US 10,100,415 B2
• Filed: 03/16/2015
• Issued: 10/16/2018
• Est. Priority Date: 03/21/2014
• Status: Active Grant

• Current Assignee: Hypersolar, Inc., Regents of the University of California (University of California)
• Original Assignee: Hypersolar, Inc.
• Inventors: Hussaini, Syed Mubeen Jawahar, McFarland, Eric W., Moskovits, Martin, Lee, Joun, Young, Tim
• Primary Examiner(s): Mendez, Zulmariam
• Application Number:
  US14/659,243
• Publication Number:
  US 20160076154A1
• Time in Patent Office: 1,310 Days
• Field of Search: 204248
• CPC Class Codes: C25B 1/04 by electrolysis of water
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: C25B 3/25 Reduction
• CPC Class Codes: C25B 9/00 Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
• CPC Class Codes: H01G 9/20 Light-sensitive devices
• CPC Class Codes: H01L 31/022425 for solar cells
• CPC Class Codes: H01L 31/032 including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
• CPC Class Codes: H01L 31/043 Mechanically stacked PV cells
• CPC Class Codes: H01L 31/0481 characterised by the composition of the encapsulation material
• CPC Class Codes: H01L 31/07 the potential barriers being only of the Schottky type
• CPC Class Codes: H01L 31/0725 Multiple junction or tandem solar cells
• CPC Class Codes: H01L 31/073 comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar cells
• CPC Class Codes: H01L 31/0749 including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
• CPC Class Codes: H01L 31/078 including different types of potential barriers provided for in two or more of groups H01L31/062 - H01L31/075
• CPC Class Codes: Y02E 10/50 Photovoltaic [PV] energy
• CPC Class Codes: Y02E 10/541 CuInSe2 material PV cells
• CPC Class Codes: Y02E 10/543 Solar cells from Group II-VI materials
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02P 20/133 Renewable energy sources, e.g. sunlight

Abstract

A multi-junction artificial photosynthetic unit includes an active element with a plurality of semiconducting layers, with metal layers deposited between the semiconductor layers appropriately forming Schottky barrier junctions or ohmic junctions with a surface of an adjacent semiconductor layer. The active element is formed within a protective structure formed of porous aluminum oxide. Successive layers of the active element can be formed within the protective structure, and additional layers and junctions can be added until desired photovoltages are achieved. A photoreactor for the production of fuels and chemicals driven by solar-powered redox reactions includes a bag reactor filled with a feedstock solution. A plurality of multi-junction photosynthetic units are placed in the feedstock solution to drive the redox reactions and produce the desired fuels and chemicals.

Claims

1. A multi junction artificial photosynthesis unit comprising:

a protective structure comprising a plurality of cavities;

a plurality of active elements, each active element formed in a corresponding cavity of the protective structure and extending between a first end and a second end, each active element comprising;

a plurality of semiconductor layers arranged such that each successive semiconductor layer stacked within the active element is configured to generate a current density substantially equal to the current density of an adjacent semiconductor layer when the active element is exposed to solar radiation; and

one or more metal layers disposed between each of the plurality of stacked semiconductor layers, each of the metal layers thereby forming a Schottky barrier junction or an ohmic junction with a surface of an adjacent semiconductor layer; and

a first electrocatalyst cap disposed at the first end of each active element and a second electrocatalyst cap disposed at the second end of each active element.

2. The multi junction artificial photosynthesis unit of claim 1, further comprising a conducting substrate joined to one face of the protective structure, the conducting substrate functioning as a working electrode for further deposition of layers within the protective structure.

3. The multi junction artificial photosynthesis unit of claim 1, wherein the protective structure is formed as a porous aluminum oxide material.

4. The multi junction artificial photosynthesis unit of claim 1, wherein one or more metal layers associated with a first semiconductor layer include a first Schottky metal layer and a first ohmic metal layer disposed on opposite sides of the first semiconductor layer.

5. The multi junction artificial photosynthesis unit of claim 4, wherein one or more metal layers associated with a second semiconductor layer include a second Schottky metal layer disposed on a surface of the second semiconductor layer adjacent to the first ohmic metal layer.

6. The multi junction artificial photosynthesis unit of claim 1, wherein a first semiconductor layer and a second semiconductor layer adjacent to the first semiconductor layer have the same composition, and wherein the second semiconductor layer has a thickness that is greater than a thickness of the first semiconductor layer to thereby enable the second semiconductor layer to generate a current density substantially equal to the current density of the first semiconductor layer when the active element is exposed to solar radiation.

7. The multi junction artificial photosynthesis unit of claim 6, further comprising one or more lower sections disposed deeper within the active element relative to the second semiconductor layer, each having a semiconductor layer of the same composition as the first and second semiconductor layers, and each semiconductor layer of each lower section being of successively greater thickness as a distance from the first semiconductor layer increases.

8. The multi junction artificial photosynthesis unit of claim 6, wherein the first and second semiconductor layers are formed from one or more of cadmium telluride (CdTe), copper indium di-selenide (CuInSe₂), selenide (CdSe), cadmium sulfide (CdS), and copper oxide (Cu₂O).

9. The multi junction artificial photosynthesis unit of claim 1, wherein at least one of the one or more metal layers forms an ohmic junction with a surface of an adjacent semiconductor layer, and is formed from one or more of Group IIB and Group III A metals.

10. The multi junction artificial photosynthesis unit of claim 1, wherein at least one of the one or more metal layers forms a Schottky barrier junction with a surface of an adjacent semiconductor layer, and is formed from one or more noble metals.

11. The multi junction artificial photosynthesis unit of claim 1, wherein the first and second electrocatalyst caps are formed from materials selected from the group consisting of transition metals, noble metals, metal oxides, conducting polymers, perovskite, and spinel type oxides.

12. The multi junction artificial photosynthesis unit of claim 1, wherein a first semiconductor layer is formed of a first semiconductor material and has a first energy bandgap, and wherein a second semiconductor layer disposed deeper within the active element relative to the first semiconductor layer is formed of a second semiconductor material and has a second energy bandgap, the second energy bandgap being less than the first energy bandgap to thereby enable the second semiconductor layer to generate a current density substantially equal to the current density of the first semiconductor layer when the active element is exposed to solar radiation.

13. The multi junction artificial photosynthesis unit of claim 12, further comprising one or more lower sections disposed deeper within the active element relative to the second semiconductor layer, each lower section having a semiconductor layer formed of semiconductor materials different from the first and second semiconductor layers, and each semiconductor layer of each lower section being of successively lower energy bandgap as a distance from the first semiconductor layer increases.

14. The multi junction artificial photosynthesis unit of claim 12, wherein the first semiconductor layer is formed from one or more of Cu₂O, ZnO, and TiO₂, and wherein the second semiconductor layer is CdSe.

15. The multi junction artificial photosynthesis unit of claim 13, wherein the semiconductor layers of the one or more lower sections are formed from one or more of CdTe and CuInSe₂.

16. The multi junction artificial photosynthesis unit of claim 1, wherein a first semiconductor layer is formed of a first semiconductor material and has a first thickness and a first energy bandgap, and wherein one or more successive semiconductor layers disposed deeper within the active element relative to the first semiconductor layer are either:

(i) formed of the first semiconductor material and have a second thickness, the second thickness being greater than the first thickness, or are

(ii) formed of a second semiconductor material and have an energy bandgap less than the first energy bandgap.

18. A photoreactor system for producing solar fuel from redox reaction products, the photoreactor system comprising:

a plurality of multi junction artificial photosynthesis units as in claim 1;

a vessel, the vessel containing the plurality of multi junction artificial photosynthesis units; and

a feedstock contained within the vessel, the plurality of multi junction artificial photosynthetic units being fully or partially submerged within the feedstock.

17. A multi junction artificial photosynthesis unit comprising:

a protective structure formed as a porous aluminum oxide and including a conducting substrate joined to one face of the protective structure; and

a plurality of active elements each formed within a corresponding pore of the protective structure, each active element comprising;

a first semiconductor layer formed of a first semiconductor material and having a first thickness and a first energy bandgap;

one or more successive semiconductor layers disposed deeper within the active element relative to the first semiconductor layer, the one or more successive semiconductor layers being either

(i) formed of the first semiconductor material and having a second thickness, the second thickness being greater than the first thickness, or

(ii) formed of a second semiconductor material and having an energy bandgap less than the first energy bandgap;

one or more metal layers disposed between each of the plurality of semiconductor layers, each of the metal layers thereby forming a Schottky barrier junction or an ohmic junction with a surface of an adjacent semiconductor layer; and

a first electrocatalyst cap disposed at the first end of each active element and a second electrocatalyst cap disposed at the second end of each active element.