Self-limiting atomic layer deposition of barium oxide and barium titanate thin films using a novel pyrrole based precursor

Acharya, Shinjita; Torgersen, Jan; Kim, Yongmin; Park, Joonsuk; Schindler, Peter; Dadlani, Anup L.; Winterkorn, Martin M.; Xu, Shicheng; Walch, Stephen P.; Usui, Takane; Schildknecht, Christian; Prinz, Fritz B.

doi:10.1039/c5tc03561a

Cited by 26 publications

(30 citation statements)

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“…At higher temperatures, Cp‐type precursors suffer from thermal decomposition and runaway growth . The lowest temperature deposition of BTO with H 2 O (180‐210°C) was a reported temperature range using a novel pyrrole‐based precursor with bonding enthalpies between the pyrrole and Ba as high as 4.9 eV …”

Section: The Ald Of Perovskitesmentioning

confidence: 99%

Atomic layer deposition of perovskites—Part 1: Fundamentals of nucleation and growth

Afif

Dadlani

Burgmann

et al. 2019

Mat Design & Process Comms

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A broad spectrum of accessible functionalities and material properties based on slight changes in crystal structure and composition makes perovskites a unique class of materials. Understanding and leveraging of its properties have resulted in its use in a myriad of applications. Today, performance and efficiency demands require these materials in miniaturized devices; hence, a precise control of perovskite synthesis in terms of thickness, crystallinity, and stoichiometry is indispensable. Atomic layer deposition (ALD) makes these requirements potentially conceivable due to the technology's unique self-limiting deposition process. Yet, not all properties of perovskites have been leveraged in the thin film regime due to limited understanding of their synthesis. In part one of a two-part review, we discuss the ALD growth of perovskite-based thin films. After explaining the specific growth characteristics of ALD perovskites, effects of process parameters, and thin film treatments on properties, we discuss an important functional perovskite strontium titanate (STO). In part two, we discuss ALD-deposited perovskites for next generation electronic applications. K E Y W O R D Satomic layer deposition, high-k, interfacial growth, nucleation and growth, perovskites, ultrathin films, piezo-electric

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Section: The Ald Of Perovskitesmentioning

confidence: 99%

Atomic layer deposition of perovskites—Part 1: Fundamentals of nucleation and growth

Afif

Dadlani

Burgmann

et al. 2019

Mat Design & Process Comms

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“…The Prinz group of Stanford University recently reported the coverage of a non-planar SiO 2 structure with BaO, a promising finding for the future deposition of high-k BTO on high-aspect-ratio substrates. 106 For investigating the crystal structure after annealing the film, XRD is by far the most widely used technique. Due to interfacial and lattice constraints and compositional inhomogeneity, ultrathin films are usually largely distorted from the ideal cubic crystal structure.…”

Section: Characterization Of Ultrathin Perovskite Filmsmentioning

confidence: 99%

“…In this section, we review characterization strategies that researchers have pursued to understand the morphology of thin-film perovskites and how they linked their findings to the obtained properties (Table 5). 15,46,[64][65][66]70,72,[76][77][78][79][80][81]83,[85][86][87]90,94,97,98,102,[104][105][106] To obtain compositional information, XPS is the most common technique. The information that can be obtained ranges from film contamination to the elemental composition within the topmost 1-10 nm of the film and its uniformity, chemical and electronic states, binding information, and depth information.…”

Section: Characterization Of Ultrathin Perovskite Filmsmentioning

confidence: 99%

“…For example, Acharya et al reported a pyrrole (py, C 4 H 4 NH)-based barium precursor (py-Ba) for the deposition of BaO and BTO. 106 They found that there is no OH species in the bulk of the film by analyzing the film using X-ray photoelectron spectroscopy (XPS), and the BaO film shows ALD characteristics. As a result, the J G of as-deposited amorphous BTO using py-Ba was very low (10 À8 A cm À2 at 1.6 V), and the dielectric constant was calculated as 35, which outperforms previously reported amorphous BTO devices.…”

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confidence: 99%

“…66 The hydroxide formation is harmful to the ALD process by restricting the self-limiting growth of BaO. 106 Moreover, the hydrogen contamination is known to increase the leakage current of the barium-containing perovskite. 107 Recent progress in a precursor that is less sensitive to impurities during ALD deposition has been reported.…”

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Process–property relationship in high-k ALD SrTiO₃ and BaTiO₃: a review

et al. 2017

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bfPerovskites exhibit a wide range of remarkable material properties that have the potential to advance various scientific fields. These properties originate in their unique structure and composition. To leverage these properties in the ultrathin film regime, atomic-level control of thickness, composition, and crystal structure will be essential for creating next-generation perovskite devices. Atomic layer deposition (ALD) has the potential to enable these design prospects. However, its future use in the field will be dependent on the quality of the link between ALD process parameters and the perovskite phase.In this overview, we present work on barium and strontium titanate (BTO and STO) ultrathin films for high-k applications. We present ALD process strategies developed and optimized to achieve both desired composition and phase, yielding high dielectric constants and low leakage currents at the same time. We discuss thermal annealing, plasma treatment, and the use of seed layers and specialized precursors to improve the properties of BTO and STO by different enhancement mechanisms. In the ultrathin film regime, the understanding of macroscopic material properties will be dependent on the knowledge of the atomic scale arrangement. In conjunction with advances in manufacturing, we therefore also discuss novel strategies and techniques for characterization that will likely be significant in establishing a valid and reliable ALD process parameter-thin film dielectric property relationship.

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Functional Perovskites by Atomic Layer Deposition – An Overview

Sønsteby

Fjellvåg

Nilsen

2017

Adv Materials Inter

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properties in thin film complex oxides and their heterostructures is still in its infancy.Functional perovskite oxide thin films have traditionally been deposited by physical, high temperature techniques, such as molecular beam epitaxy (MBE) and pulsed laser deposition (PLD). While these methods can provide films of very high structural quality, they do not offer deposition of conformal film on complex structures while maintaining control of stoichiometry. Chemical deposition techniques were long thought unsuitable for deposition of complex systems with high structural quality. This has changed dramatically over the last two decades. One of the most important techniques to emerge in this area has been atomic layer deposition (ALD).In this short review we aim to summarize the perovskite and ABO 3 -oxides, down to the ilmenite structure, that have been deposited using the ALD technique. The review includes work done over the last 20 years, and covers all oxide perovskites with ferromagnetic, piezoelectric and ferroelectric functionality known to have been deposited by ALD ( Table 1). The origin of the properties in these specific structures is briefly discussed, followed by a complete listing of the known systems. Perovskite heterostructures with new properties and combinations of properties are brought up, before thoughts on possible future work in the field concludes the paper. Why Atomic Layer Deposition?The ALD technique was pioneered independently in both Russia and Finland during the 1960s and 70s, and its history was thoroughly described by Puurunen in 2014. [4] The technique has been comprehensively discussed in several review papers over the last years. The first commercial application was to deposit zinc sulfide, used for electroluminescent display panels. The number of materials with known deposition routes was very limited for the first 20 years, before it exploded in the 1990s and still continues to grow. At the time of the review written by Miikkulainen et al. in 2013, binary oxides of most of the natural elements had been reported, as well as many nitrides, sulfides and fluorides (Figure 2). [5] As the community has embraced the possibility of growing epitaxial films of high chemical and structural quality, systems that are even more complex have been deposited, including materials with ternary, quaternary and even quinary compositions.The advantages and drawbacks of ALD as a thin film deposition technique have been reviewed several times the The last 20 years have seen a massive increase in reports on complex oxides with functional properties synthesized by atomic layer deposition (ALD). Many of these compounds have perovskite or perovskite-related structures, and exhibit a range of electric and magnetic properties. This short review summarizes the current status of functional perovskites and ABO 3 compounds down to the ilmenite structure prepared by ALD, focusing on ferromagnetism and ferro-and piezoelectricity. All perovskite-related compounds known to have been deposited by ALD down to the ilmeni...

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Self-limiting atomic layer deposition of barium oxide and barium titanate thin films using a novel pyrrole based precursor

Abstract: Self-limiting growth of high quality binary BaO and BaTiO3 using a novel class of Ba precursor at lowest temperature ever reported and shown to cover non planar structures.

Cited by 26 publications

References 47 publications

Atomic layer deposition of perovskites—Part 1: Fundamentals of nucleation and growth

Atomic layer deposition of perovskites—Part 1: Fundamentals of nucleation and growth

Process–property relationship in high-k ALD SrTiO₃ and BaTiO₃: a review

Functional Perovskites by Atomic Layer Deposition – An Overview

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Self-limiting atomic layer deposition of barium oxide and barium titanate thin films using a novel pyrrole based precursor

Abstract: Self-limiting growth of high quality binary BaO and BaTiO3 using a novel class of Ba precursor at lowest temperature ever reported and shown to cover non planar structures.

Cited by 26 publications

References 47 publications

Atomic layer deposition of perovskites—Part 1: Fundamentals of nucleation and growth

Atomic layer deposition of perovskites—Part 1: Fundamentals of nucleation and growth

Process–property relationship in high-k ALD SrTiO3 and BaTiO3: a review

Functional Perovskites by Atomic Layer Deposition – An Overview

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Product

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Process–property relationship in high-k ALD SrTiO₃ and BaTiO₃: a review