Band-Edge Potentials of n-Type and p-Type GaN

Beach, J. D.; Collins, R. T.; Turner, John A.

doi:10.1149/1.1577542

Cited by 106 publications

(119 citation statements)

References 37 publications

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“…[6][7] For example, GaN is one of the nitride semiconductors that have been studied for photocatalytic applications [8][9][10][11] because its CBM and VBM straddle the hydrogen reduction (H + /H 2 ) and water oxidation (H 2 O/O 2 ) potentials. Although GaN has a large bandgap (3.4 eV), indium alloying to form InGaN can tune the bandgap from the ultraviolet to the near infrared region 12 encompassing the entire solar spectrum.…”

Section: Introductionmentioning

confidence: 99%

Si/InGaN Core/Shell Hierarchical Nanowire Arrays and their Photoelectrochemical Properties

et al. 2012

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Three dimensional hierarchical nanostructures were synthesized by the halide chemical vapor deposition (HCVD) of InGaN nanowires on Si wire arrays. Single phase InGaN nanowires grew vertically on the sidewalls of Si wires and acted as a high surface area photoanode for solar water splitting. Electrochemical measurements showed that the photocurrent density with hierarchical Si/InGaN nanowire arrays increased by 5 times compared to the photocurrent density with InGaN nanowire arrays grown on planar Si (1.23 V vs RHE). High resolution transmission electron microscopy showed that InGaN nanowires are stable after 15 hours of illumination. These measurements show that Si/InGaN hierarchical nanostructures are a viable high surface area geometry for stable solar water splitting. KEYWORDS:Hierarchical nanostructure, InGaN nanowire, Si wire, photoanode, solar water splitting IntroductionPhotolysis of water with semiconductor materials has been investigated as a clean and renewable energy conversion process by storing solar energy in chemical bonds such as hydrogen. [1][2][3] Since Fujishima and Honda 4 reported the capability of water splitting with TiO 2 , metal oxide semiconductors have been studied extensively due to their stability under photo-anodic conditions. [5][6] However, the valence band of metal oxide semiconductors consists mainly of O 2p orbitals resulting in a low energy maximum (around +3 V vs NHE compared to +1.23 V vs NHE for the water oxidation reaction). This leads to a significant loss in energy from the large difference in potential between the valence band and water oxidation reaction. In addition, lowering the metal oxide bandgap energy for visible light absorption generally comes at the cost of moving the conduction band minimum (CBM) towards lower potentials than the hydrogen reduction potential which cannot perform spontaneous solar water splitting.On the other hand, metal nitrides have less positive valence band maximum (VBM) potentials than metal oxides because N 2p orbitals have smaller ionization energies than O 2p orbitals. [6][7] For example, GaN is one of the nitride semiconductors that have been studied for photocatalytic applications [8][9][10][11] because its CBM and VBM straddle the hydrogen reduction (H + /H 2 ) and water oxidation (H 2 O/O 2 ) potentials. Although GaN has a large bandgap (3.4 eV), indium alloying to form InGaN can tune the bandgap from the ultraviolet to the near infrared region 12 encompassing the entire solar spectrum. The In 0.5 Ga 0.5 N alloy has a bandgap of around 2.0 eV which is desirable for overall water splitting considering the overpotential for the water oxidation reaction. [13][14] Moses et al. 15 calculated that the VBM of InGaN alloy increases in energy almost linearly with indium composition. Therefore, the InGaN alloy was suggested to accomplish spontaneous overall water splitting with up to 50% indium incorporation since both the CBM and VBM can satisfy the energetic requirements. Experimentally, single crystalline In x Ga 1-x N nanowire...

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Section: Introductionmentioning

confidence: 99%

Si/InGaN Core/Shell Hierarchical Nanowire Arrays and their Photoelectrochemical Properties

et al. 2012

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“…[6][7][8] In addition, the bandgap energy of GaN-based materials can be varied from about 0.65 to 6.0 eV by alloying them with InN and AlN, which enables us to design various functional photoelectrodes not only for spectral matching of solar light but also for the electrochemical reduction of CO 2 to carbohydrate. 9 One of the common approaches to improving conversion efficiency is to form nanostructures on the photoelectrode surface in order to increase its surface area.…”

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confidence: 99%

Correlation between Structural and Photoelectrochemical Properties of GaN Porous Nanostructures Formed by Photo-Assisted Electrochemical Etching

Kumazaki¹,

Watanabe²,

Yatabe³

et al. 2014

J. Electrochem. Soc.

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We investigated the correlation between structural and photoelectrochemical properties of GaN porous nanostructures formed by photo-assisted electrochemical etching. The porous nanostructures were formed during light irradiation of the top-surface of homo-epitaxial layers grown on freestanding GaN substrates. The pore depth, wall thickness, and surface morphology of porous nanostructures were strongly influenced by the way holes generated by the light irradiation were supplied. Such structural features influenced the optical properties of GaN porous nanostructures. The photoluminescence peaks measured on GaN porous nanostructures were shifted to higher energies because of the quantum confinement in the thin GaN walls between pores. Formation of porous nanostructure decreased the photoreflectance of the GaN surface, and the smallest reflectance was obtained from the porous sample having large pores on its surface after the ultrathin layer with small pores had been removed by surface-etching. The photoelectrochemical response measured on GaN porous nanostructures in a NaCl electrolyte were drastically enhanced by the unique features of those structures, such as low photoreflectance and large surface area. The largest photocurrents were obtained from the sample from which H 3 PO 4 treatment had removed the ultrathin layer without thinning the pore walls. Photoelectrochemical systems based on semiconductor photoelectrodes have recently attracted much attention due to their potential use in the next generation of green technologies such as water splitting for fuel cells, artificial photosynthesis, and so on.1-5 Among the photoelectrode materials, GaN is one of the most attractive because of its chemical stability and its potential to achieve direct photoelectrolysis by solar power without the consumption of electric power. [6][7][8] In addition, the bandgap energy of GaN-based materials can be varied from about 0.65 to 6.0 eV by alloying them with InN and AlN, which enables us to design various functional photoelectrodes not only for spectral matching of solar light but also for the electrochemical reduction of CO 2 to carbohydrate. 9 One of the common approaches to improving conversion efficiency is to form nanostructures on the photoelectrode surface in order to increase its surface area. Most reported GaN nanostructures have been made using selective-area growth 10,11 or a dry etching process such as reactive ion etching. 12,13 There are, however, severe limitations on increasing the density of nanostructures because most approaches use lithography for defining the size and position of the nanostructures. And when a dry etching process is involved, the etching damage induced by ion bombardment is not negligible [14][15][16] and could significantly degrade the photoelectrochemical efficiency.One alternative approach is an electrochemical-fabrication process, which can form various semiconductor nanostructures in a self-assembled fashion. The most well-known application of an electrochemical process is the formation...

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“…Gallium Nitride (GaN), a wide, direct band gap semiconductor, has been shown to be stable under visible photolysis and has the right band edge energetics [1]. Tandem cells based on III-V materials have been shown to have very high efficiency for spontaneous photoelectrochemical (PEC) water splitting (≈ 12%) [2], but their applicability as single gap cells for direct photoelectrochemical water splitting has been limited by the unfavorable band energetics [3].…”

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confidence: 99%

Visible-light absorption and large band-gap bowing of GaN1−xSbxfrom first principles

et al. 2011

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Band-Edge Potentials of n-Type and p-Type GaN

Cited by 106 publications

References 37 publications

Si/InGaN Core/Shell Hierarchical Nanowire Arrays and their Photoelectrochemical Properties

Si/InGaN Core/Shell Hierarchical Nanowire Arrays and their Photoelectrochemical Properties

Correlation between Structural and Photoelectrochemical Properties of GaN Porous Nanostructures Formed by Photo-Assisted Electrochemical Etching

Visible-light absorption and large band-gap bowing of GaN1−xSbxfrom first principles

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