Electron acceleration and capture device for preserving excess kinetic energy to drive electrochemical reduction reactions

Patent metadata

Field	Value
Publication number	US-11342131-B2
Application number	US-201816036464-A
Country	US
Kind code	B2
Filing date	Jul 16, 2018
Priority date	Jul 17, 2017
Publication date	May 24, 2022
Grant date	May 24, 2022

Abstract

Disclosed is a semiconductor-liquid junction based photoelectrochemical (PEC) cell for the unassisted solar splitting of water into hydrogen and oxygen gas, the solar-driven reduction of CO2 to higher-order hydrocarbons, and the solar-driven synthesis of NH3. The disclosed system can employ a photocathode based upon wurtzite hexagonal semiconductors that can be tailored with proper band alignment for the redox potentials for water, CO2 reduction, and NH3 production, and with bandgap energy for maximum solar absorption. The design maximizes the carrier collection efficiency by leveraging spontaneous and piezoelectric polarization in these materials systems to generate hot electrons within the photocathode. These electrons have sufficient excess energy, preserved at a designed energy capture region, to overcome the kinetic overpotential (surface chemistry limitation) required for the reactions to occur at a high rate.

First claim

What is claimed:

1. A photocathode for producing hydrogen gas and hydrogen containing compounds from reactants within a liquid and supporting electrolytes which reduces the overpotential required to drive the reactions, the photocathode comprising:
an electrical contact that collects carriers;
a semiconducting region having a first total polarization vector P 1 , and being operatively associated with the contact;
a light absorption region adapted to create electron-hole pairs, the light absorption region being adjacent to the semiconducting region, forming a first interface with the semiconducting region, and having a second total polarization vector P 2 greater than or equal to P 1 ;
an electron acceleration region adjacent to the light absorption region, the electron acceleration region having an electron acceleration region bandgap, the electron acceleration region forming a second interface with the light absorption region, the electron acceleration region having a third total polarization vector P 3 greater than the second total polarization vector P 2 such that a negative polarization charge is formed at the second interface which creates an electric field that is adapted to accelerate electrons within the electron acceleration region away from the second interface; and
an energy capture region having a fourth total polarization vector P 4 adjacent to the electron acceleration region, the energy capture region forming a third interface with the electron acceleration region and having an energy capture region bandgap that is larger than the electron acceleration region bandgap such that the potential energy of the conduction band of the energy capture region is larger than the potential energy of the conduction band of the electron acceleration region, the interface charge at the third interface and the space charge in the energy capture region configured to form a junction between the liquid and the energy capture region that depletes the energy capture region of majority carriers such that the resulting electric field in the energy capture region directs electrons in the energy capture region toward the liquid;
whereby the photocathode is configured such that kinetic energy gained by the electrons in the electron acceleration region is captured as potential energy in the energy capture region so as to facilitate chemical reduction reactions.

2. The photocathode according to claim 1 , wherein the second total polarization vector P 2 of the light absorption region is greater than the first total polarization vector P 1 of the semiconducting region, forming a negative polarization charge at the first interface and creating an electric field that depletes the light absorption region such that holes are collected by drift and diffusion at the contact and electrons are collected from the light absorption region by drift into the electron acceleration region.

3. The photocathode according to claim 1 , wherein the second total polarization vector P 2 of the light absorption region is the same as the first total polarization vector P 1 of the semiconducting region, and the amount of doping of both the light absorption and the semiconducting regions is equal, forming a junction that is quasi-neutral such that holes are collected by diffusion at the contact and electrons are collected by diffusion at the interface of the light absorption region and the electron acceleration region.

4. The photocathode according to claim 1 , wherein the liquid is comprised of three components: a solvent, reactants for the chemical reaction at the surface of the photocathode, and a supporting electrolyte salt.

5. The photocathode according to claim 1 , further comprising a polar substrate with the direction of epitaxial growth forming an acute angle greater than or equal to zero with the [000 1 ] direction.

6. The photocathode according to claim 5 , wherein the energy capture region has a fourth total polarization vector P 4 greater than the third total polarization vector P 3 , forming a negative polarization charge at the third interface and creating an electric field that accelerates the electrons toward the liquid.

7. The photocathode according to claim 6 , wherein the light absorption region is comprised of a II-VI alloy or III-Nitride alloy having an equal or larger bandgap than a bandgap of the semiconducting region, the alloy being suitable for light absorption of the solar spectrum;
wherein the electron acceleration region is comprised of a II-VI or III-Nitride alloy of larger bandgap than the light absorption region; and
wherein the energy capture region is comprised of a II-VI or III-Nitride alloy with larger bandgap than the electron acceleration region.

8. The photocathode according to claim 5 , wherein the semiconducting region is comprised of an alloy having a wurtzite hexagonal crystal structure, the alloy comprising either:
N with at least one element selected from the Group III elements consisting of In, Al and Ga (III-Nitride alloy); or
at least one Group II element selected from the group consisting of Mg, Zn, Cd, with at least one Group VI element selected from the group consisting of O, S, Se, Te (II-VI alloy).

9. The photocathode according to claim 5 , wherein the semiconducting region is doped p-type with a density of Mg atoms greater than or equal to 1×10 19 cm −3 and the light absorption region, electron acceleration region, and energy capture region are doped p-type with a density of Mg atoms less than or equal to 1×10 19 cm −3 .

10. The photocathode according to claim 9 , wherein the second total polarization vector P 2 of the light absorption region is the same as the first total polarization vector P 1 of the semiconducting region, and the doping of the semiconducting region is at a larger concentration than the doping of the light absorption region, forming a junction that has a depleted light absorption region adapted to sustain an electric field such that holes are collected by drift and diffusion at the contact and electrons are collected by drift at the interface of the light absorption region and the electron acceleration region in the electron acceleration region.

11. The photocathode according to claim 9 , wherein the semiconducting region is comprised of In x Ga 1−x N with a thickness in the range of 100 nm to 1000 nm and with x in the range of 0.2 to 0.22, the light absorption region is comprised of In 0.2 Ga 0.8 N with a thickness in the range of 100 nm to 300 nm, the electron acceleration region is comprised of In 0.18 Ga 0.82 N with a thickness in the range of 50 nm to 100 nm, and the energy capture region is comprised of In x Ga 1−x N with x in the range of 0 to 0.16 and thickness in the range 5 nm to 100 nm.

12. The photocathode according to claim 9 , wherein the polar substrate is doped p-type and the contact to the semiconducting region is formed through the polar substrate.

13. The photocathode according to claim 9 , wherein the polar substrate is n-type GaN and the contact to the semiconducting region is formed through the polar substrate using a tunnel junction comprised of a GaN region adjacent to the n-type GaN substrate doped n-type with a density of Si atoms greater than 1×10 19 cm −3 , an InN region with thickness in the range of 1 to 3 nm, and the first semiconducting region doped p-type with a density of Mg atoms greater than 1×10 19 cm −3 .

14. The photocathode according to claim 5 , wherein the semiconducting region has a free hole concentration greater than or equal to 1×10 17 cm −3 and the light absorption region, electron acceleration region, and energy capture region each have free hole

Assignees

• Us Army Res Lab
• Us Army

Inventors

• Wraback Michael
• Sampath Anand V
• Shen Paul
• Parameshwaran Vijay S

Classifications

• Y02P20/133

  Renewable energy sources, e.g. sunlight · CPC title

• Y02E10/542

  Dye sensitized solar cells · CPC title

• H01G9/2054

  comprising a semiconductor electrode comprising AII-BVI compounds, e.g. CdTe, CdSe, ZnTe, ZnSe, with or without impurities, e.g. doping materials (H01G9/2027 takes precedence) · CPC title

• C25B1/55

  Photoelectrolysis · CPC title

• H01G9/205 Primary

  comprising a semiconductor electrode comprising AIII-BV compounds with or without impurities, e.g. doping materials · CPC title