skip to main content


Title: Amorphous inorganic semiconductors for the development of solar cell, photoelectrocatalytic and photocatalytic applications
Amorphous inorganic semiconductors have attracted growing interest due to their unique electrical and optical properties that arise from their intrinsic disordered structure and thermodynamic metastability. Recently, amorphous inorganic semiconductors have been applied in a variety of new technologies, including solar cells, photoelectrocatalysis, and photocatalysis. It has been reported that amorphous phases can improve both efficiency and stability in these applications. While these phenomena are well established, their mechanisms have long remained unclear. This review first introduces the general background of amorphous inorganic semiconductor properties and synthesis. Then, the recent successes and current challenges of amorphous inorganic semiconductor-based materials for applications in solar cells, photoelectrocatalysis, and photocatalysis are addressed. In particular, we discuss the mechanisms behind the remarkable performances of amorphous inorganic semiconductors in these fields. Finally, we provide insightful perspectives into further developments for applications of amorphous inorganic semiconductors.  more » « less
Award ID(s):
1914713 1803495 1903990 1914562
NSF-PAR ID:
10226169
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Chemical Society Reviews
ISSN:
0306-0012
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. The discovery of oxide electronics is of increasing importance today as one of the most promising new technologies and manufacturing processes for a variety of electronic and optoelectronic applications such as next-generation displays, batteries, solar cells, memory devices, and photodetectors[1]. The high potential use seen in oxide electronics is due primarily to their high carrier mobilities and their ability to be fabricated at low temperatures[2]. However, since the majority of oxide semiconductors are n-type oxides, current applications are limited to unipolar devices, eventually developing oxide-based bipolar devices such as p-n diodes and complementary metal-oxide semiconductors. We have contributed to a wide range of oxide semiconductors and their electronics and optoelectronic device applications. Particularly, we have demonstrated n-type oxide-based thin film transistors (TFT), integrating In 2 O 3 -based n-type oxide semiconductors from binary cation materials to ternary cation species including InZnO, InGaZnO (IGZO), and InAlZnO. We have suggested channel/metallization contact strategies to achieve stable and high TFT performance[3, 4], identified vacancy-based native defect doping mechanisms[5], suggested interfacial buffer layers to promote charge injection capability[6], and established the role of third cation species on the carrier generation and carrier transport[7]. More recently, we have reported facile manufacturing of p-type SnOx through reactive magnetron sputtering from a Sn metal target[8]. The fabricated p-SnOx was found to be devoid of metallic phase of Sn from x-ray photoelectron spectroscopy and demonstrated stable performance in a fully oxide-based p-n heterojunction together with n-InGaZnO. The oxide-based p-n junctions exhibited a high rectification ratio greater than 10 3 at ±3 V, a low saturation current of ~2x10 -10 , and a small turn-on voltage of -0.5 V. In this presentation, we review recent achievements and still remaining issues in transition metal oxide semiconductors and their device applications, in particular, bipolar applications including p-n heterostructures and complementary metal-oxide-semiconductor devices as well as single polarity devices such as TFTs and memristors. In addition, the fundamental mechanisms of carrier transport behaviors and doping mechanisms that govern the performance of these oxide-based devices will also be discussed. ACKNOWLEDGMENT This work was supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 20011028) by KRISS. K.N. was supported by Basic Science Research Program (NRF-2021R11A1A01051246) through the NRF Korea funded by the Ministry of Education. REFERENCES [1] K. Nomura et al. , Nature, vol. 432, no. 7016, pp. 488-492, Nov 25 2004. [2] D. C. Paine et al. , Thin Solid Films, vol. 516, no. 17, pp. 5894-5898, Jul 1 2008. [3] S. Lee et al. , Journal of Applied Physics, vol. 109, no. 6, p. 063702, Mar 15 2011, Art. no. 063702. [4] S. Lee et al. , Applied Physics Letters, vol. 104, no. 25, p. 252103, 2014. [5] S. Lee et al. , Applied Physics Letters, vol. 102, no. 5, p. 052101, Feb 4 2013, Art. no. 052101. [6] M. Liu et al. , ACS Applied Electronic Materials, vol. 3, no. 6, pp. 2703-2711, 2021/06/22 2021. [7] A. Reed et al. , Journal of Materials Chemistry C, 10.1039/D0TC02655G vol. 8, no. 39, pp. 13798-13810, 2020. [8] D. H. Lee et al. , ACS Applied Materials & Interfaces, vol. 13, no. 46, pp. 55676-55686, 2021/11/24 2021. 
    more » « less
  2. Abstract

    Perovskite solar cells (PSCs) have attracted much attention as efficiencies go beyond 22%. To achieve these impressive numbers, the PSC scientific community is working to improve both the perovskite optoelectronic properties, and, importantly, the interfacial properties of the adjacent electron selective contacts (ESLs). Improvements in both fronts have happened concurrently and are responsible for these rapid efficiency gains. Here, the authors review the recent advances in understanding the role of ESLs on performance improvements. ESLs can be prepared from either organic and inorganic semiconductors, or a combination of both, and their key characteristics are summarized in detail. Current state‐of‐the‐art PSCs employ fully inorganic ESLs made of a thin mesoporous TiO2or a planar SnO2, with reported certified efficiencies of 22.7 and 20.9%, respectively. While TiO2shows excellent performance in the short term, it has also been shown to induce solar cell degradation due to its UV absorption properties. Understanding ESLs has been instrumental in the rapid development of PSCs; however, some challenges remain in terms of understanding the role of different ESLs on the long‐term stability of the devices.

     
    more » « less
  3. Hybrid organic–inorganic perovskites (HOIPs) have become an important class of semiconductors for solar cells and other optoelectronic applications. Electron–phonon coupling plays a critical role in all optoelectronic devices, and although the lattice dynamics and phonon frequencies of HOIPs have been well studied, little attention has been given to phonon lifetimes. We report high-precision momentum-resolved measurements of acoustic phonon lifetimes in the hybrid perovskite methylammonium lead iodide (MAPI), using inelastic neutron spectroscopy to provide high-energy resolution and fully deuterated single crystals to reduce incoherent scattering from hydrogen. Our measurements reveal extremely short lifetimes on the order of picoseconds, corresponding to nanometer mean free paths and demonstrating that acoustic phonons are unable to dissipate heat efficiently. Lattice-dynamics calculations using ab initio third-order perturbation theory indicate that the short lifetimes stem from strong three-phonon interactions and a high density of low-energy optical phonon modes related to the degrees of freedom of the organic cation. Such short lifetimes have significant implications for electron–phonon coupling in MAPI and other HOIPs, with direct impacts on optoelectronic devices both in the cooling of hot carriers and in the transport and recombination of band edge carriers. These findings illustrate a fundamental difference between HOIPs and conventional photovoltaic semiconductors and demonstrate the importance of understanding lattice dynamics in the effort to develop metal halide perovskite optoelectronic devices.

     
    more » « less
  4. The discovery of oxide electronics is of increasing importance today as one of the most promising new technologies and manufacturing processes for a variety of electronic and optoelectronic applications such as next-generation displays, batteries, solar cells, and photodetectors. The high potential use seen in oxide electronics is due primarily to their high carrier mobilities and their ability to be fabricated at low temperatures. However, since the majority of oxide semiconductors are n-type oxides, current applications are limited to unipolar devices, eventually developing oxide-based bipolar devices such as p-n diodes and complementary metal-oxide semiconductors. We have contributed to wide range of oxide semiconductors and their electronics and optoelectronic device applications. Particularly, we have demonstrated n-type oxide-based thin film transistors (TFT), integrating In2O3-based n-type oxide semiconductors from binary cation materials to ternary cation species including InZnO, InGaZnO (IGZO), and InAlZnO. We have suggested channel/metallization contact strategies to achieve stable TFT performance, identified vacancy-based native defect doping mechanisms, suggested interfacial buffer layers to promote charge injection capability, and established the role of third cation species on the carrier generation and carrier transport. More recently, we have reported facile manufacturing of p-type SnOx through reactive magnetron sputtering from a Sn metal target. The fabricated p-SnOx was found to be devoid of metallic phase of Sn from x-ray photoelectron spectroscopy and demonstrated stable performance in a fully oxide based p-n heterojunction together with n-InGaZnO. The oxide-based p-n junctions exhibited a high rectification ratio greater than 103 at ±3 V, a low saturation current of ~2x10-10, and a small turn-on voltage of -0.5 V. With all the previous achievements and investigations about p-type oxide semiconductors, challenges remain for implementing p-type oxide realization. For the implementation of oxide-based p-n heterojunctions, the performance needs to be further enhanced. The current on/off ration may be limited, in our device structure, due to either high reverse saturation current (or current density) or non-ideal performance. In this study, two rational strategies are suggested to introduce an “intrinsic” layer, which is expected to reduce the reverse saturation current between p-SnOx and n-IGZO and hence increase the on/off ratio. The carrier density of n-IGZO is engineered in-situ during the sputtering process, by which compositionally homogeneous IGZO with significantly reduced carrier density is formed at the interface. Then, higher carrier density IGZO is formed continuously on the lower carrier density IGZO during the sputtering process without any exposure of the sample to the air. Alternatively, heterogeneous oxides of MgO and SiO2 are integrated into between p-SnOx and n-IGZO, by which the defects on the surface can be passivated. The interfacial properties are thoroughly investigated using transmission electron microscopy and atomic force microscopy. The I-V characteristics are compared between the set of devices integrated with two types of “intrinsic” layers. The current research results are expected to contribute to the development of p-type oxides and their industrial application manufacturing process that meets current processing requirements, such as mass production in p-type oxide semiconductors. 
    more » « less
  5. Delafossite structured ternary nitrides, ABN 2 , have been of recent experimental investigation for applications such as tandem solar and photoelectrochemical cells. We present a thorough first principles computational investigation of their stability, electronic structure, and optical properties. Nine compounds, where A = Cu, Ag, Au and B = V, Nb, Ta, were studied. For three of these compounds, CuTaN 2 , CuNbN 2 , and AgTaN 2 , our computations agree well with experimental results. Optimized lattice parameters, formation energies, and mechanical properties have been computed using the generalized gradient approximation (GGA). Phonon density of states computed at zero-temperature shows that all compounds are dynamically unstable at low temperatures. Including finite-temperature anharmonic effects stabilizes all compounds at 300 K, with the exception of AgVN 2 . Analysis of Crystal Orbital Hamiltonian Populations (COHP) provides insight into the bonding and antibonding characters of A–N and B–N pairs. Instability at low temperatures can be attributed to strong A–N antibonding character near the Fermi energy. B–N bonding is found to be crucial in maintaining stability of the structure. AgVN 2 is the only compound to display significant B–N antibonding below the Fermi energy, as well as the strongest degree of A–N antibonding, both of which provide explanation for the sustained instability of this compound up to 900 K. Hybrid functional calculations of electronic and optical properties show that real static dielectric constants in the semiconductors are related to corresponding band gaps through the Moss relation. CuTaN 2 , CuNbN 2 , AgTaN 2 , AgNbN 2 , AgVN 2 , AuTaN 2 , and AuNbN 2 exhibit indirect electronic band gaps while CuVN 2 and AuVN 2 are metallic. Imaginary parts of the dielectric function are characterized by d–d interband transitions in the semiconductors and d–d intraband transitions in the metals. Four compounds, CuTaN 2 , CuNbN 2 , AgTaN 2 , and AgNbN 2 , are predicted to exhibit large light absorption in the range of 1.0 to 1.7 eV, therefore making these materials good candidates for solar-energy conversion applications. Two compounds, AuTaN 2 and AuNbN 2 , have band gaps and absorption onsets near the ideal range for obtaining high solar-cell conversion efficiency, suggesting that these compounds could become potential candidates as absorber materials in tandem solar cells or for band-gap engineering by alloying. 
    more » « less