Semiconducting two-dimensional (2D) materials are studied intensively because of their promising performance in diverse applications from electronics to energy storage and catalysis. Recently, HfS2 and ZrS2 have emerged as potential rivals for the commonly studied 2D semiconductors such as MoS2 and WSe2, but their use is hindered by the difficulty of producing continuous films. Herein, we report the first atomic layer deposition (ALD) processes for HfS2 and ZrS2 using HfCl4 and ZrCl4 with H2S as the precursors. We demonstrate the deposition of uniform and continuous films on a range of substrates with accurately controlled thicknesses ranging from a few monolayers to tens of nanometers. The use of semiconductor industry-compatible precursors and temperatures (approximately 400 °C) enables facile upscaling of the process. The deposited HfS2 and ZrS2 films are crystalline, smooth, and stoichiometric with oxygen as the main impurity. As an important step toward applications of HfS2 and ZrS2, we show that their sensitivity toward oxidation can be overcome by minimizing the impurities in the reactor and by depositing a protective Al x Si y O z layer on the top without a vacuum break. Finally, we demonstrate HfS2 and ZrS2 photodetectors exhibiting good performance and stable operation in ambient conditions. Photoresponsivity comparable to thin films or even single flakes of HfS2 or ZrS2 deposited at much higher temperatures is achieved, although the response speed seems to be limited by photogating, as is common for 2D photodetectors. We expect the first ALD processes for HfS2 and ZrS2 to enable further exploration of these materials for various semiconductor applications.

Compared to the most well-known 2D material, graphene, which is a semi-metal, the semiconducting 2H phase of MoS 2 is advantageous in having a band gap suitable for electronic applications. In bulk form, MoS 2 has an indirect band gap of 1.3 eV, which increases as a function of decreasing film thickness. In monolayer MoS 2 (thickness ≈0.6 nm), the band gap becomes direct with a width of 1.8 eV. [1] Importantly, to meet the requirements of different applications, properties of MoS 2 and other TMDCs can be tuned by controlling the thickness, [1] doping and alloying, [5][6][7][8] surface modification and functionalization, [9][10][11] strain, [12,13] and by creating heterostructures with other 2D materials. [6,[14][15][16] The appealing properties of TMDCs have led to a wide range of proposed applications. MoS 2 has been extensively studied as a channel material in conventional field-effect transistors, [17][18][19][20][21] as well as phototransistors and other optoelectronic devices. [16,21,22] The 2D structure of TMDCs plays a crucial role in possible applications relying on more exotic quantum phenomena, such as valleytronics. [23,24] MoS 2 has also shown promise in, for example, catalysis, [25] batteries, [26] photovoltaics, [27] sensors, [28] and medicine. [29] The production of high-quality, large-area MoS 2 films with a thickness controllable down to a monolayer, as required in many of the aforementioned applications, still remains a major challenge. Additionally, in many cases, the processing temperature should be kept as low as possible in order to avoid damaging sensitive substrates, such as polymers or nanostructures. Initially, flakes of monolayer MoS 2 were produced from natural MoS 2 crystals using micromechanical exfoliation, a topdown method capable of producing high-quality monolayers, albeit with poor throughput as well as limited control over flake thickness and dimensions. [4,30,31] Liquid-phase exfoliation of bulk crystals, on the other hand, offers good scalability, but often suffers from limited flake size, poor crystallinity, or contamination. [4,31,32] Bottom-up methods offer a more controllable way to produce MoS 2 films. High-quality MoS 2 thin films are most commonly deposited by chemical vapor deposition (CVD) or sulfurization of metal or metal oxide thin films. The most common Molybdenum disulfide (MoS 2 ) is a semiconducting 2D material, which has evoked wide interest due to its unique properties. However, the lack of controlled and scalable methods for the production of MoS 2 films at low temperatures remains a major hindrance on its way to applications. In this work, atomic layer deposition (ALD) is used to deposit crystalline MoS 2 thin films at a relatively low temperature of 300 °C. A new molybdenum precursor, Mo(thd) 3 (thd = 2,2,6,6-tetramethylheptane-3,5-dionato), is synthesized, characterized, and used for film deposition with H 2 S as the sulfur precursor. Self-limiting growth with a low growth rate of ≈0.025 Å cycle −1 , straightforward thickness control, and large-area uni...

Semiconducting 2D materials, such as SnS , hold immense potential for many applications ranging from electronics to catalysis. However, deposition of few-layer SnS films has remained a great challenge. Herein, continuous wafer-scale 2D SnS films with accurately controlled thickness (2 to 10 monolayers) are realized by combining a new atomic layer deposition process with low-temperature (250 °C) postdeposition annealing. Uniform coating of large-area and 3D substrates is demonstrated owing to the unique self-limiting growth mechanism of atomic layer deposition. Detailed characterization confirms the 1T-type crystal structure and composition, smoothness, and continuity of the SnS films. A two-stage deposition process is also introduced to improve the texture of the films. Successful deposition of continuous, high-quality SnS films at low temperatures constitutes a crucial step toward various applications of 2D semiconductors.

Atomic layer deposition (ALD) enables the deposition of numerous materials in thin film form, yet there are no ALD processes for metal iodides. Herein, we demonstrate an ALD process for PbI2, a metal iodide with a two-dimensional (2D) structure that has applications in areas such as photodetection and photovoltaics. This process uses lead silylamide Pb­(btsa)2 and SnI4 as precursors and works at temperatures below 90 °C, on a variety of starting surfaces and substrates such as polymers, metals, metal sulfides, and oxides. The starting surface defines the crystalline texture and morphology of the PbI2 films. Rough substrates yield porous PbI2 films with randomly oriented 2D layers, whereas smooth substrates yield dense films with 2D layers parallel to the substrate surface. Exposure to light increases conductivity of the ALD PbI2 films which enables their use in photodetectors. The films can be converted into a CH3NH3PbI3 halide perovskite, an important solar cell absorber material. For various applications, ALD offers advantages such as ability to uniformly coat large areas and simple means to control film thickness. We anticipate that the chemistry exploited in the PbI2 ALD process is also applicable for ALD of other metal halides.

Optoelectronic materials can source, detect, and control light wavelengths ranging from gamma and x rays to ultraviolet, visible, and infrared regions. Optoelectronic devices are usually systems that transduce electricity to optical signal or vice versa. Optoelectronic devices include many modern necessities such as lamps, displays, lasers, solar cells, and various photodetectors. Some important research topics in the field of optoelectronics materials are development of new materials, new technologies for fabricating materials, and design of device structures. Atomic layer deposition (ALD) is a technology that was developed in the early 1970s for manufacturing high-quality luminescent and dielectric films to be used in AC-driven thin film electroluminescent (TFEL) displays. Monochromic yellow-black displays based on a ZnS:Mn luminescent layer have been manufactured industrially using ALD since the mid-1980s. Multicolor displays (green-yellow-red) were successfully realized by filtering the broad emission band of ZnS:Mn or adding another luminescent material, e.g., green-emitting ZnS:Tb or SrS:Ce. However, applicable full-color AC TFEL devices could not be developed because of the lack of an efficient deep blue-emitting phosphor. Currently, the most promising application area in TFEL displays is transparent displays, which are commonly used in various vehicles. In the mid-1980s, epitaxial III-V semiconductors were studied using ALD. It was shown that manufacturing real epitaxial [atomic layer epitaxy (ALE)] films is possible for different III (Al, Ga, In) and V (N, P, As) materials. The advantages of ALE processing compared to more traditional metalorganic chemical vapor deposition or molecular beam epitaxy methods have remained low, however, and ALE is not used on a large scale. Research continues to be carried out using ALE, especially with nitride films. Thin film solar cells have continuously received attention in ALD research. ALD films may be used as both an absorber (CdTe, SnS) and a passivation [In2S3, Zn(O,S)] material. However, in the solar cell field, the real industrial-level use is in passivation of silicon cells. Thin ALD Al2O3 film effectively passivates all types of silicon cells and improves their efficiency. Transition metal dichalcogenides are emerging 2D materials that have potential uses as channel materials in field-effect transistors, as well as phototransistors and other optoelectronic devices. The problem with achieving large-scale use of these 2D materials is the lack of a scalable, low-temperature process for fabricating high-quality, large-area films. ALD is proposed as a solution for these limitations. This review covers all of these ALD applications in detail.