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

All highly-efficient organic–inorganic halide perovskite (OIHP) solar cells to date are made of polycrystalline perovskite films which contain a high density of defects, including point and extended imperfections. The imperfections in OIHP materials play an important role in the process of charge recombination and ion migration in perovskite solar cells (PSC), which heavily influences the resulting device energy conversion efficiency and stability. Here we review the recent advances in passivation of imperfections and suppressing ion migration to achieve improved efficiency and highly stable perovskite solar cells. Due to the ionic nature of OIHP materials, the defects in the photoactive films are inevitably electrically charged. The deep level traps induced by particular charged defects in OIHP films are major non-radiative recombination centers; passivation by coordinate bonding, ionic bonding, or chemical conversion have proven effective in mitigating the negative impacts of these deep traps. Shallow level charge traps themselves may contribute little to non-radiative recombination, but the migration of charged shallow level traps in OIHP films results in unfavorable band bending, interfacial reactions, and phase segregation, influencing the carrier extraction efficiency. Finally, the impact of defects and ion migration on the stability of perovskite solar cells is described.

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Imperfections and their passivation in halide perovskite solar cells

Semiconductor nanowires (NWs) have been studied extensively for over two decades for their novel electronic, photonic, thermal, electrochemical and mechanical properties. This comprehensive review article summarizes major advances in the synthesis, characterization, and application of these materials in the past decade. Developments in the understanding of the fundamental principles of "bottom-up" growth mechanisms are presented, with an emphasis on rational control of the morphology, stoichiometry, and crystal structure of the materials. This is followed by a discussion of the application of nanowires in i) electronic, ii) sensor, iii) photonic, iv) thermoelectric, v) photovoltaic, vi) photoelectrochemical, vii) battery, viii) mechanical, and ix) biological applications. Throughout the discussion, a detailed explanation of the unique properties associated with the one-dimensional nanowire geometry will be presented, and the benefits of these properties for the various applications will be highlighted. The review concludes with a brief perspective on future research directions, and remaining barriers which must be overcome for the successful commercial application of these technologies.

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25th Anniversary Article: Semiconductor Nanowires – Synthesis, Characterization, and Applications

Plasma-assisted atomic layer deposition (ALD) is an energy-enhanced method for the synthesis of ultra-thin films with A-level resolution in which a plasma is employed during one step of the cyclic deposition process. The use of plasma species as reactants allows for more freedom in processing conditions and for a wider range of material properties compared with the conventional thermally-driven ALD method. Due to the continuous miniaturization in the microelectronics industry and the increasing relevance of ultra-thin films in many other applications, the deposition method has rapidly gained popularity in recent years, as is apparent from the increased number of articles published on the topic and plasma-assisted ALD reactors installed. To address the main differences between plasma-assisted ALD and thermal ALD, some basic aspects related to processing plasmas are presented in this review article. The plasma species and their role in the surface chemistry are addressed and different equipment configurations, including radical-enhanced ALD, direct plasma ALD, and remote plasma ALD, are described. The benefits and challenges provided by the use of a plasma step are presented and it is shown that the use of a plasma leads to a wider choice in material properties, substrate temperature, choice of precursors, and processing conditions, but that the processing can also be compromised by reduced film conformality and plasma damage. Finally, several reported emerging applications of plasma-assisted ALD are reviewed. It is expected that the merits offered by plasma-assisted ALD will further increase the interest of equipment manufacturers for developing industrial-scale deposition configurations such that the method will find its use in several manufacturing applications.

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Plasma-Assisted Atomic Layer Deposition: Basics, Opportunities, and Challenges

The reduction in electronic recombination losses by the passivation of silicon surfaces is a critical enabler for high-efficiency solar cells. In 2006, aluminum oxide (Al2O3) nanolayers synthesized by atomic layer deposition (ALD) emerged as a novel solution for the passivation of p- and n-type crystalline Si (c-Si) surfaces. Today, high efficiencies have been realized by the implementation of ultrathin Al2O3 films in laboratory-type and industrial solar cells. This article reviews and summarizes recent work concerning Al2O3 thin films in the context of Si photovoltaics. Topics range from fundamental aspects related to material, interface, and passivation properties to synthesis methods and the implementation of the films in solar cells. Al2O3 uniquely features a combination of field-effect passivation by negative fixed charges, a low interface defect density, an adequate stability during processing, and the ability to use ultrathin films down to a few nanometers in thickness. Although various methods can be used to synthesize Al2O3, this review focuses on ALD—a new technology in the field of c-Si photovoltaics. The authors discuss how the unique features of ALD can be exploited for interface engineering and tailoring the properties of nanolayer surface passivation schemes while also addressing its compatibility with high-throughput manufacturing. The recent progress achieved in the field of surface passivation allows for higher efficiencies of industrial solar cells, which is critical for realizing lower-cost solar electricity in the near future.

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Status and prospects of Al2O3-based surface passivation schemes for silicon solar cells

Thin Al2O3 films with a thickness of 7–30 nm synthesized by plasma-assisted atomic layer deposition (ALD) were used for surface passivation of crystalline silicon (c-Si) of different doping concentrations. The level of surface passivation in this study was determined by techniques based on photoconductance, photoluminescence, and infrared emission. Effective surface recombination velocities of 2 and 6 cm/s were obtained on 1.9 Ω cm n-type and 2.0 Ω cm p-type c-Si, respectively. An effective surface recombination velocity below 1 cm/s was unambiguously obtained for nearly intrinsic c-Si passivated by Al2O3. A high density of negative fixed charges was detected in the Al2O3 films and its impact on the level of surface passivation was demonstrated experimentally. The negative fixed charge density results in a flat injection level dependence of the effective lifetime on p-type c-Si and explains the excellent passivation of highly B-doped c-Si by Al2O3. Furthermore, a brief comparison is presented between the ...

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Silicon surface passivation by atomic layer deposited Al2O3

This work has been supported by the Australian Research
Council and the State of Lower Saxony.

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Formation rates of iron-acceptor pairs in crystalline silicon

We examine nonrecombination active minority-carrier trapping centers in crystalline silicon using a lock-in infrared camera technique. Application of a simple trapping model to the injection-dependent lifetime data obtained from the infrared emission signal results in high-resolution mappings (spatial resolution=170μm) of the trap density and the energy level. Measurements on Czochralski-grown silicon wafers show striation-related inhomogeneities of the trap density and a very homogeneous distribution of energy levels.

Mapping of trap densities and energy levels in semiconductors using a lock-in infrared camera technique

We image the lifetime distribution of multicrystalline silicon wafers by means of calibrated measurements of the free-carrier emission using an infrared camera. The spatially resolved lifetime measurements are performed as a function of the light-generated excess carrier density, showing a pronounced increase in lifetime with decreasing injection density at very low injection levels. Two theoretical models are applied to describe the abnormal lifetime increase: (i) minority-carrier trapping and (ii) depletion region modulation around charged bulk defects. The trapping model is found to give better agreement with the experimental data. By fitting the trapping model to each point of the lifetime image recorded at different injection levels, we generate a trap density mapping. On multicrystalline silicon wafers we find a clear correlation between trap and dislocation density mappings.

Defect imaging in multicrystalline silicon using a lock-in infrared camera technique

This paper gives a review of some recent developments in the field of contactless silicon wafer characterization techniques based on lifetime spectroscopy and infrared imaging. In the first part of the contribution, we outline the status of different lifetime spectroscopy approaches suitable for the identification of impurities in silicon and discuss—in more detail—the technique of temperature- and injection-dependent lifetime spectroscopy. The second part of the paper focuses on the application of infrared cameras to analyze spatial inhomogeneities in silicon wafers. By measuring the infrared signal absorbed or emitted from light-generated free excess carriers, high-resolution recombination lifetime mappings can be generated within seconds to minutes. In addition, mappings of non-recombination-active trapping centers can be deduced from injection-dependent infrared lifetime images. The trap density has been demonstrated to be an important additional parameter in the characterization and assessment of solar-grade multicrystalline silicon wafers, as areas of increased trap density tend to deteriorate during solar cell processing.

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Peter Pohl

Papers

Silicon surface passivation by atomic layer deposited Al2O3

Formation rates of iron-acceptor pairs in crystalline silicon

Mapping of trap densities and energy levels in semiconductors using a lock-in infrared camera technique

Defect imaging in multicrystalline silicon using a lock-in infrared camera technique

Advances in Contactless Silicon Defect and Impurity Diagnostics Based on Lifetime Spectroscopy and Infrared Imaging