Facile rearrangement of molecular layer deposited metalcone thin films by electron beam irradiation for area selective atomic layer deposition

Lee, Seung Hwan; Baek, Geon Ho; Kim, Hye mi; Kim, Yong Hwan; Park, Jin‐Seong

doi:10.1039/d1dt01380g

Cited by 8 publications

(10 citation statements)

References 51 publications

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“…By contrast, the carbon content drastically increased over 94.4 at% at 600 °C annealing temperature, which is attributed to the formation and enlargement of graphitic carbon. [ 15 ] Due to the low oxidation energy, low bond dissociation energy, and volatility of products with the formation of molecules which are compounds of indium and ligands after annealing, indium can be evaporated. [ 14a ] The as‐dep indicone has an amorphous structure and is transformed to nanocrystalline graphite after thermal annealing.…”

Section: Resultsmentioning

confidence: 99%

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Thermally Annealed Molecular Layer‐Deposited Indicone: Structural Analysis and Area Selective Deposition Application

Lee

Baek

Yang

et al. 2022

Adv Materials Inter

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A half pitch can be decreased by increasing numerical aperture (N.A.), immersion lithography, decrement of the k-value, and multiple patterning using an ArF source. [2] However, since the remaining ArF source for lithography dramatically increases the cost of device fabrication, lithography using an extreme ultraviolet (EUV) source was introduced for high volume manufacturing. However, a number of requirements including a pellicle, photoresist (PR), and numerical aperture for the EUV process have to be developed. In addition, as the device structure becomes smaller and more complicated, the number of vias exceeds billions and the probability of failure during the top-down process for device fabrication increases. Area selective deposition (ASD) as a bottom-up process is a patterning method used to deposit a thin film only in a desired area, which can complement the disadvantages of the topdown process by simplifying the process, attaining errorless alignment, increasing yield, and reducing the cost and probability of failure. [3] In the manufacturing process of semiconductor devices, a number of ASD processes have been devised such as self-aligned gate, contact and via, fully self-aligned via (FSAV), and self-aligned blocking.For realizing a bottom-up process, area selective atomic layer deposition (AS-ALD) has been researched vigorously using chemistry. [4] The ALD process has principles based on the surface chemistry. [5] At least two kinds of precursors are sequentially injected to the reactor and form a monolayer via a self-limited reaction. The precursors chemically adsorb and react on the functional groups of the surface, generating a thin film with repeated cycles. Because of the self-limiting reaction and surface reaction, the ALD process is advantageous for depositing a conformal and uniform film over 3D structures and a large area, exhibiting excellent thickness control on the nanoscale, and allowing various kinds of thin films such as metals, oxides, nitrides, and sulfides. The film growth through ALD depends on the surface chemistry, where the characteristic chemical reaction occurs with a specific chemical state of the surface. In other words, AS-ALD can be induced by modulating the precursors, reactants, surface constitution, and functional groups of the surface. [6] However, it is still deliberated how ASD should be employed during the production of semiconductor devices in thousands of processes.Semiconductor devices have become smaller, more complicated, and structuralized in three dimensions. Area selective deposition is one of the promising bottom-up process techniques for self-alignment or improved overlay to achieve errorless alignment. The surface chemistry is crucial to adjust precursor adsorption. In this research, graphitic carbon fabricated by molecular layer deposition is utilized for inhibiting precursor adsorption. An indicone film, which has an indium-based metalcone structure, is fabricated using bis(trimethysily)-amidodiethylindium and hydroquinone. The structure of the indicone ...

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Section: Resultsmentioning

confidence: 99%

“…The MLD films which contain benzene rings can be transformed to a 2D‐like carbon film which consists of graphitic carbon by a thermal annealing process or electron beam irradiation. [ 15 ] In addition, MLD films can be used as inhibitors to delay film growth with a deficiency of functional groups on the surface.…”

Section: Introductionmentioning

confidence: 99%

Thermally Annealed Molecular Layer‐Deposited Indicone: Structural Analysis and Area Selective Deposition Application

Lee

Baek

Yang

et al. 2022

Adv Materials Inter

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“…First, all elements except carbon hinder the molecular rearrangement, acting as impurities. In the indicone film, the metal evaporation could originate from the relatively lower bond dissociation energy of the indium–oxygen bond (320.1 kJ/mol) and the lower oxidation energy of indium (0.34 V) compared with the aluminum–oxygen bond (511 kJ/mol) and the oxidation energy of aluminum (1.662 V). − In addition, the indium can be removed readily due to the monovalent In + and ligands left unreacted in the indicone films. , In the annealing process, indium can evaporate in the form of In(C 2 H 5 ) and InOH. As a result, ordered graphitic carbon that is mainly composed of sp 2 carbon is generated from the indicone film.…”

Section: Resultsmentioning

confidence: 99%

Dry-Etchable Molecular Layer-Deposited Inhibitor Using Annealed Indicone Film for Nanoscale Area-Selective Deposition

Lee

Kim

Baek

et al. 2021

ACS Appl. Mater. Interfaces

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In semiconductor production, the technology node of a device is becoming extremely small below 5 nm. Area selective deposition (ASD) is a promising technique for creating improved overlay or self-alignment, remedying a conventional top-down method. However, the conventional materials and process (selfassembled monolayer, polymer and carbon film fabricated by chemical vapor deposition, and spin coating) for ASD are not suitable for highly conformal deposition. Thus, we investigated a new strategy to deposit conformal films in ASD by molecular layer deposition (MLD). The MLD processes were conducted for an indicone film deposited by INCA-1 (bis(trimethysily)amidodiethyl indium) and hydroquinone (HQ), as well as an alucone film deposited by TMA (trimethylaluminum) and HQ. After thermal heat treatment of the MLD films, variations in thickness, refractive index, and constituent elements of the annealed MLD films were investigated. The indicone film was used as an inhibiting layer for ASD and was etchable with a dry-etching process. The reactive ion etching process on annealed indicone film was optimized according to plasma power, gas concentration, and working pressure. Ruthenium (Ru) ALD was then performed on the annealed MLD films to investigate nucleation delaying cycles and inhibiting properties. A patterned substrate with an MLD/Si line was created via the RIE process, which was allowed to observe the selectivity of the annealed MLD films. In addition, a patterned substrate of SiO 2 /annealed indicone/Mo was used to investigate the Ruselective ALD at the nanoscale. The Ru thin film was selectively deposited on the Mo side-wall surface of a 3D trench structure. The growth of the Ru film was inhibited selectively on an annealed indicone surface of approximately 5 nm.

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“…Based on the collected results, we propose one of the potential chemical reactions associated with low-energy electron exposure to the MALD TMA/HQ hybrid thin film. It is suspected that the dehydrogenation process during electron exposure can induce longitudinal cross-linking between hydroquinone, 16 which potentially can lead to the formation of graphitic carbon networks, 17 causing the solubility switching of the inorganic-organic hybrid thin films.…”

Section: Chemical Reactions Associated With Low-energy Electron Expos...mentioning

confidence: 99%

Chemical reactions induced by low-energy electron exposure on a novel inorganic-organic hybrid dry EUV photoresist deposited by molecular atomic layer deposition (MALD)

Hwang

Woo

et al. 2022

International Conference on Extreme Ultraviolet Lithography 2022

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Herein, we investigated the chemical reactions associated with low-energy electron exposures on an inorganic-organic hybrid thin film system deposited using molecular atomic layer deposition (MALD) for EUV photoresist applications. Using the hybrid thin films consisting of trimethylaluminum (TMA) and hydroquinone (HQ), we determined the critical doses and thickness contrast of the hybrid materials at various electron energies (up to 400 eV). The custom-built in-situ Fourier-Transform Infrared (FTIR) spectroscopy system, equipped with an electron flood gun and gas residual analyzer (RGA), was employed to monitor the chemical changes induced by low-energy electrons in the hybrid thin films. Based on the in-situ FTIR and RGA results, potential chemical reaction mechanisms responsible for the change in solubility of the TMA/HQ material are proposed.

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Facile rearrangement of molecular layer deposited metalcone thin films by electron beam irradiation for area selective atomic layer deposition

Abstract: Metalcone films can be rearranged from amorphous structures to 2D-like carbon by electron beam irradiation. The irradiated indicone (HQ) film can be used as an inhibitor for selective deposition delaying 20 cycles of ALD of ZnO.

Cited by 8 publications

References 51 publications

Thermally Annealed Molecular Layer‐Deposited Indicone: Structural Analysis and Area Selective Deposition Application

Thermally Annealed Molecular Layer‐Deposited Indicone: Structural Analysis and Area Selective Deposition Application

Dry-Etchable Molecular Layer-Deposited Inhibitor Using Annealed Indicone Film for Nanoscale Area-Selective Deposition

Chemical reactions induced by low-energy electron exposure on a novel inorganic-organic hybrid dry EUV photoresist deposited by molecular atomic layer deposition (MALD)

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