reported under AM1.5 (AM: air mass) illumination, this efficiency is not sufficient to meet realistic specifications for commercialization. The need to improve the light-to-electricity conversion efficiency requires the implementation of new materials and the exploration of new device architectures. Polymer-based photovoltaic cells are thin-film devices fabricated in the metal-insulator-metal configuration sketched in Figure 1a. The absorbing and charge-separating bulk-heterojunction layer with a thickness of approximately 100 nm is sandwiched between two charge-selective electrodes; a transparent bilayer electrode comprising poly(3,4-ethylenedioxylenethiophene):polystyrene sulfonic acid (PEDOT:PSS) on indium tin oxide (ITO) glass for collecting the holes and a lower-work-function metal (here, Al) for collecting the electrons. The work-function difference between the two electrodes provides a built-in potential that breaks the symmetry, thereby providing a driving force for the photogenerated electrons and holes toward their respective electrodes. Because of optical interference between the incident (from the ITO side) and back-reflected light, the intensity of the light is zero at the metallic (Al) electrode; Figure 1a shows a schematic representation of the spatial distribution of the squared optical electric-field strength. [9–11] Thus, a relatively large fraction of the active layer is in a dead-zone in which the photogeneration of carriers is significantly reduced. Moreover, this effect causes more electron–hole pairs to be produced near the ITO/PEDOT:PSS electrode, a distribution which is known to reduce the photovoltaic conversion efficiency. [12,13] This “optical interference effect” is especially important for thin-film structures where layer thicknesses are comparable to the absorption depth and the wavelength of the incident light, as is the case for photovoltaic cells fabricated from semiconducting polymers. In order to overcome these problems, one might simply increase the thickness of the active layer to absorb more light. Because of the low mobility of the charge carriers in the polymer:C60 composites, however, the increased internal resistance of thicker films will inevitably lead to a reduced fill factor. An alternative approach is to change the device architecture with the goal of spatially redistributing the light intensity inside the device by introducing an optical spacer between the active layer and the Al electrode as sketched in Figure 1a. [11] Although this revised architecture would appear to solve the problem, the prerequisites for an ideal optical spacer limit the choice of materials: the layer must be a good acceptor and an electron-transport material with a conduction band edge lower in energy than that of the lowest unoccupied molecular orbital (LUMO) of C60; the LUMO must be above (or close to) the Fermi energy of the collecting metal electrode; and it must be transparent to light with wavelengths within the solar spectrum.

New Architecture for High-Efficiency Polymer Photovoltaic Cells Using Solution-Based Titanium Oxide as an Optical Spacer

Solution-processed hybrid organic–inorganic perovskites (HOIPs) exhibit long electronic carrier diffusion lengths, high optical absorption coefficients and impressive photovoltaic device performance. Recent results allow us to compare and contrast HOIP charge-transport characteristics to those of III–V semiconductors — benchmarks of photovoltaic (and light-emitting and laser diode) performance. In this Review, we summarize what is known and unknown about charge transport in HOIPs, with particular emphasis on their advantages as photovoltaic materials. Experimental and theoretical findings are integrated into one narrative, in which we highlight the fundamental questions that need to be addressed regarding the charge-transport properties of these materials and suggest future research directions. The charge transport properties of hybrid organic—inorganic perovskites, which can explain their excellent photovoltaic performance, are reviewed through an integrated summary of experimental and theoretical findings. The potential origins of these properties are discussed and future research directions are indicated.

Hybrid organic—inorganic perovskites: low-cost semiconductors with intriguing charge-transport properties

Atomic layer deposition (ALD) is gaining attention as a thin film deposition method, uniquely suitable for depositing uniform and conformal films on complex three-dimensional topographies. The deposition of a film of a given material by ALD relies on the successive, separated, and self-terminating gas–solid reactions of typically two gaseous reactants. Hundreds of ALD chemistries have been found for depositing a variety of materials during the past decades, mostly for inorganic materials but lately also for organic and inorganic–organic hybrid compounds. One factor that often dictates the properties of ALD films in actual applications is the crystallinity of the grown film: Is the material amorphous or, if it is crystalline, which phase(s) is (are) present. In this thematic review, we first describe the basics of ALD, summarize the two-reactant ALD processes to grow inorganic materials developed to-date, updating the information of an earlier review on ALD [R. L. Puurunen, J. Appl. Phys. 97, 121301 (2005)], and give an overview of the status of processing ternary compounds by ALD. We then proceed to analyze the published experimental data for information on the crystallinity and phase of inorganic materials deposited by ALD from different reactants at different temperatures. The data are collected for films in their as-deposited state and tabulated for easy reference. Case studies are presented to illustrate the effect of different process parameters on crystallinity for representative materials: aluminium oxide, zirconium oxide, zinc oxide, titanium nitride, zinc zulfide, and ruthenium. Finally, we discuss the general trends in the development of film crystallinity as function of ALD process parameters. The authors hope that this review will help newcomers to ALD to familiarize themselves with the complex world of crystalline ALD films and, at the same time, serve for the expert as a handbook-type reference source on ALD processes and film crystallinity.

Crystallinity of inorganic films grown by atomic layer deposition: Overview and general trends

A new chapter in the long and distinguished history of perovskites is being written with the breakthrough success of metal halide perovskites (MHPs) as solution-processed photovoltaic (PV) absorbers. The current surge in MHP research has largely arisen out of their rapid progress in PV devices; however, these materials are potentially suitable for a diverse array of optoelectronic applications. Like oxide perovskites, MHPs have ABX3 stoichiometry, where A and B are cations and X is a halide anion. Here, the underlying physical and photophysical properties of inorganic (A = inorganic) and hybrid organic–inorganic (A = organic) MHPs are reviewed with an eye toward their potential application in emerging optoelectronic technologies. Significant attention is given to the prototypical compound methylammonium lead iodide (CH3NH3PbI3) due to the preponderance of experimental and theoretical studies surrounding this material. We also discuss other salient MHP systems, including 2-dimensional compounds, where rele...

Intriguing Optoelectronic Properties of Metal Halide Perovskites

Halide perovskites have recently emerged as promising materials for low-cost, high-efficiency solar cells. The efficiency of perovskite-based solar cells has increased rapidly, from 3.8% in 2009 to 19.3% in 2014, by using the all-solid-state thin-film architecture and engineering cell structures with mixed-halide perovskites. The emergence of perovskite solar cells revolutionized the field not only because of their rapidly increased efficiency, but also flexibility in material growth and architecture. The superior performance of the perovskite solar cells suggested that perovskite materials possess intrinsically unique properties. In this review, we summarize recent theoretical investigations into the structural, electrical, and optical properties of halide perovskite materials in relation to their applications in solar cells. We also discuss some current challenges of using perovskites in solar cells, along with possible theoretical solutions.

Halide perovskite materials for solar cells: a theoretical review

First-Principles Study of the Structural and the Electronic Properties of the Lead-Halide-Based Inorganic-Organic perovskites (CH3NH3)PbX3 and CsPbX3 (X = Cl, Br, I)

The photoluminescence (PL) origin of bright blue emission arising from intrinsic states in graphene quantum dots (GQDs) is investigated. The bright PL of intercalatively acquired GQDs is attributed to favorably formed subdomains composed of four to seven carbon hexagons. Random and harsh oxidation which hinders the energetically favorable formation of subdomains causes weak and redshifted PL.

Intrinsic Photoluminescence Emission from Subdomained Graphene Quantum Dots.

Optical absorption, photoluminescence and Raman scattering of lead-halide based inorganic-organic perovskite semiconductors were measured under quasi-hydrostatic pressure at room temperature. For the 3D perovskite semiconductor, (CH 3 NH 3 )PbBr 3 , the free exciton photoluminescence band exhibits red-shifts with pressure, and jumps to a higher energy by 0.07 eV at 0.8 GPa, which is associated with a phase transition from a cubic to an orthorhombic structure confirmed by Raman scattering. Above the phase transition pressure, the exciton band shows blue-shifts with further increasing pressure, and eventually disappears above 4.7 GPa. The results are compared with those for the 2D perovskite semiconductor, (C 4 H 9 NH 3 ) 2 PbI 4 . First principles pseudopotential calculations were performed to investigate changes in octahedral distortion and electronic band structures with pressure. The calculations have explained the origins of the intriguing changes in the electronic states with pressure in view of bonding characters between atomic orbitals in octahedra.

Optical properties and structural phase transitions of lead-halide based inorganic–organic 3D and 2D perovskite semiconductors under high pressure

Reflectance of conducting poly(3,4-ethylenedioxythiophene)

Controlling and sensing spin states of magnetic molecules at the single-molecule level is essential for spintronic molecular device applications. Here, we demonstrate that spin states of Co–porphyrin on Au(111) can be reversibly switched over by binding and unbinding of the NO molecule and can be sensed using scanning tunneling microscopy and spectroscopy (STM and STS). Before NO exposure, Co–porphryin showed a clear zero-bias peak, a signature of Kondo effect in STS, whereas after NO exposures, it formed a molecular complex, NO–Co–porphyrin, that did not show any zero-bias feature, implying that the Kondo effect was switched off by binding of NO. The Kondo effect could be switched back on by unbinding of NO through single-molecule manipulation or thermal desorption. Our density functional theory calculation results explain the observations with pairing of unpaired spins in dz2 and ppπ* orbitals of Co–porphyrin and NO, respectively. Our study opens up ways to control molecular spin state and Kondo effect ...

Yun Hee Chang

Papers

First-Principles Study of the Structural and the Electronic Properties of the Lead-Halide-Based Inorganic-Organic perovskites (CH3NH3)PbX3 and CsPbX3 (X = Cl, Br, I)

Intrinsic Photoluminescence Emission from Subdomained Graphene Quantum Dots.

Optical properties and structural phase transitions of lead-halide based inorganic–organic 3D and 2D perovskite semiconductors under high pressure

Reflectance of conducting poly(3,4-ethylenedioxythiophene)

Switching and Sensing Spin States of Co–Porphyrin in Bimolecular Reactions on Au(111) Using Scanning Tunneling Microscopy