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1.
Small Methods ; 8(1): e2300933, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37882332

RESUMO

Implementing high-performance ultraviolet C photodetectors (UVC PDs) based on ß-Ga2 O3 films is challenging owing to the anisotropic crystal symmetry between the epitaxial films and substrates. In this study, highly enhanced state-of-the-art photoelectrical performance is achieved using single-domain epitaxy of monoclinic ß-Ga2 O3 films on a hexagonal sapphire substrate. Unlike 3D ß-Ga2 O3 films with twin domains, 2D ß-Ga2 O3 films exhibit a single domain with a smooth surface and low concentration of point defects, which enable efficient charge separation by suppressing boundary-induced recombination. Furthermore, a tailored anti-reflection coating (ARC) is adopted as a light-absorbing medium to improve charge generation. The tailored nanostructure, which features a gradient refractive index, not only substantially reduces the reflection, but also suppresses the surface leakage current as a passivation layer. This study provides fundamental insights into the single-domain epitaxy of ß-Ga2 O3 films and the application of ARC for the development of high-performance UVC PDs.

2.
ACS Appl Mater Interfaces ; 14(22): 25781-25791, 2022 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-35623063

RESUMO

Microlight-emitting diode (Micro-LED) is the only display production technology capable of meeting the high-performance requirements of future screens. However, it has significant obstacles in commercialization due to etching loss and efficiency reduction caused by the singulation process, in addition to expensive costs and a significant amount of time spent on transfer. Herein, multiple-sapphire nanomembrane (MSNM) technology has been developed that enables the rapid transfer of arrays while producing micro-LEDs without the need for any singulation procedure. Individual micro-LEDs of tens of µm size were formed by the pendeo-epitaxy and coalescence of GaN grown on 2 µm width SNMs spaced with regular intervals. We have successfully fabricated micro-LEDs of different sizes including 20 × 20 µm2, 40 × 40 µm2, and 100 × 100 µm2, utilizing the membrane design. It was confirmed that the 100 × 100 µm2 micro-LED manufactured with MSNM technology not only relieved stress by 80.6% but also reduced threading dislocation density by 58.7% compared to the reference sample. It was proven that micro-LED arrays of varied chip sizes using MSNM were all transferred to the backplane. A vertical structure LED device could be fabricated using a 100 × 100 µm2 micro-LED chip, and it was confirmed to have a low operation voltage. Our work suggests that the development of the MSNM technology is promising for the commercialization of micro-LED technology.

3.
ACS Appl Mater Interfaces ; 14(4): 5598-5607, 2022 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-35040629

RESUMO

α-Gallium oxide, with its large band gap energy, is a promising material for utilization in power devices. Sapphire, which has the same crystal structure as α-Ga2O3, has been used as a substrate for α-Ga2O3 epitaxial growth. However, lattice and thermal expansion coefficient mismatches generate a high density of threading dislocations (TDs) and cracks in films. Here, we demonstrated the growth of α-Ga2O3 films with reduced TD density and residual stress on microcavity-embedded sapphire substrates (MESS). We fabricated the two types of substrates with microcavities: diameters of 1.5 and 2.2 µm, respectively. We confirmed that round conical-shaped cavities with smaller diameters are beneficial for the lateral overgrowth of α-Ga2O3 crystals with lower TD densities by mist chemical vapor deposition. We could obtain crack-free high-crystallinity α-Ga2O3 films on MESS, while the direct growth on a bare sapphire substrate resulted in an α-Ga2O3 film with a number of cracks. TD densities of α-Ga2O3 films on MESS with 1.5 and 2.2 µm cavities were measured to be 1.77 and 6.47 × 108 cm-2, respectively. Furthermore, cavities in MESS were certified to mitigate the residual stress via the redshifted Raman peaks of α-Ga2O3 films. Finally, we fabricated Schottky diodes based on α-Ga2O3 films grown on MESS with 1.5 and 2.2 µm cavities, which exhibited high breakdown voltages of 679 and 532 V, respectively. This research paves the way to fabricating Schottky diodes with high breakdown voltages based on high-quality α-Ga2O3 films.

4.
Nanoscale ; 13(23): 10356-10364, 2021 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-34105564

RESUMO

Crystalline silicon nanoparticles at the nanometer scale have been attracting great interest in many different optoelectronic applications such as photovoltaic and light-emitting-diode devices. Formation, crystallization, and size control of silicon nanoparticles in nonharsh and nontoxic environments are highly required to achieve outstanding optoelectronic characteristics. The existing methods require high temperature, use of HF solution, and an additional process for the uniform redistribution of nanoparticles on the substrate and there are difficulties in controlling the size. Herein, we report a new self-assembly method that applies the controlled extremely low plasma ion energy near the sputtering threshold energy in rare gas environments as nonharsh and nontoxic environments. This method produces silicon nanoparticles by crystallization nucleation directly at the surface of the amorphous film via plasma surface interactions. It is evidently observed that the nucleation and growth rates of the crystalline silicon nanoparticles are promoted by the enhanced plasma ion energy. The crystalline silicon nanoparticle size is tailored to the nanometer scale by the plasma ion energy control.

5.
Sci Adv ; 6(24): eaba4942, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32577521

RESUMO

The structural transformations of graphene defects have been extensively researched through aberration-corrected transmission electron microscopy (AC-TEM) and theoretical calculations. For a long time, a core concept in understanding the structural evolution of graphene defects has been the Stone-Thrower-Wales (STW)-type bond rotation. In this study, we show that undercoordinated atoms induce bond formation and breaking, with much lower energy barriers than the STW-type bond rotation. We refer to them as mediator atoms due to their mediating role in the breaking and forming of bonds. Here, we report the direct observation of mediator atoms in graphene defect structures using AC-TEM and annular dark-field scanning TEM (ADF-STEM) and explain their catalytic role by tight-binding molecular dynamics (TBMD) simulations and image simulations based on density functional theory (DFT) calculations. The study of mediator atoms will pave a new way for understanding not only defect transformation but also the growth mechanisms in two-dimensional materials.

6.
Sci Rep ; 10(1): 7506, 2020 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-32371935

RESUMO

A discrete core-shell-like micro-light-emitting diode (micro-LED) array was grown on a 100 nm-thick sapphire nano-membrane array without harmful plasma etching for chip singulation. Due to proper design for the sapphire nano-membrane array, an array of multi-faceted micro-LEDs with size of 4 µm × 16 µm was grown. Threading dislocation density in the micro-LED formed on sapphire nano-membrane was reduced by 59.6% due to the sapphire nano-membranes, which serve as compliant substrates, compared to GaN formed on a planar substrate. Enhancements in internal quantum efficiency by 44% and 3.3 times higher photoluminescence intensity were also observed from it. Cathodoluminescence emission at 435 nm was measured from c-plane multiple quantum wells (MQWs), whereas negligible emissions were detected from semi-polar sidewall facets. A core-shell-like MQWs were formed on all facets, hopefully lowering concentration of non-radiative surface recombination centers and reducing leakage current paths. This study provides an attractive platform for micro-LEDs by using sapphire nano-membrane.

7.
RSC Adv ; 10(12): 6822-6830, 2020 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-35493897

RESUMO

Amorphous carbon (a-C) films have attracted significant attention due to their reliable structures and superior mechanical, chemical and electronic properties, making them a strong candidate as an etch hard mask material for the fabrication of future integrated semiconductor devices. Density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations were performed to investigate the energetics, structure, and mechanical properties of the a-C films with an increasing sp3 content by adjusting the atomic density or hydrogen content. A drastic increase in the bulk modulus is observed by increasing the atomic density of the a-C films, which suggests that it would be difficult for the films hardened by high atomic density to relieve the stress of the individual layers within the overall stack in integrated semiconductor devices. However, the addition of hydrogen into the a-C films has little effect on increasing the bulk modulus even though the sp3 content increases. For the F blocking nature, the change in the sp3 content by both atomic density and H concentration makes the diffusion barrier against the F atom even higher and suppresses the F diffusion, indicating that the F atom would follow the diffusion path passing through the sp2 carbon and not the sp3 carbon due to the significantly high barrier. For the material design of a-C films with adequate doped characteristics, our results can provide a new straightforward strategy to tailor the a-C films with excellent mechanical and other novel physical and chemical properties.

8.
Sci Rep ; 9(1): 18661, 2019 Dec 09.
Artigo em Inglês | MEDLINE | ID: mdl-31819126

RESUMO

In this study, multicolor photodetectors (PDs) fabricated by using bulk p-i-n-based visible GaAs and near-infrared InGaAs structures were monolithically integrated through a high-throughput epitaxial lift-off (ELO) process. To perform multicolor detection in integrated structures, GaAs PDs were transferred onto InGaAs PDs by using a Y2O3 bonding layer to simultaneously detect visible and near-infrared photons and minimize the optical loss. As a result, it was found that the GaAs top PD and InGaAs bottom PD were vertically aligned without tilting in x-ray diffraction (XRD) measurement. A negligible change in the dark currents for each PD was observed in comparison with reference PDs through electrical characterization. Furthermore, through optical measurements and simulation, photoresponses were clearly revealed in the visible and near-infrared band for the material's absorption region, respectively. Finally, we demonstrated the simultaneous multicolor detection of the visible and near-infrared region,which implies individual access to each PD without mutual interference. These results are a significant improvement for the fabrication of multicolor PDs that enables the formation of bulk-based multicolor PDs on a single substrate with a high pixel density and nearly perfect vertical alignment for high-resolution multicolor imaging.

9.
Sci Rep ; 9(1): 18961, 2019 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-31831828

RESUMO

Amorphous carbon (a-C) films have received significant attention due to their reliable structures and superior mechanical, chemical and electronic properties, making them a strong candidate as a hard mask material. We investigated the energetics, structure, and electronic and mechanical properties of the B, N, and Cl doped a-C films based on density functional theory (DFT) calculation. Our DFT calculated results clearly show that introducing B and N atoms into a-C films makes the bulk modulus slightly reduced as a function of the concentration increases. Interestingly, it is noted that introducing Cl atom into a-C films makes the bulk modulus is drastically reduced, which suggests that the films softened by Cl doping would relieve residual stress of the individual layers within the overall stacks in integrated semiconductor devices. These requirements become more important and increasingly more challenging to meet as the device integrity grows. In the perspective of F blocking nature, B doping into a-C films pulls in and captures the F atom due to the strong bonding nature of B‒F bond than C-F bond. Unlike the B doping, for the N doped a-C film, F atom has extremely large diffusion barrier of 4.92 eV. This large diffusion barrier is attributed to the electrostatically repulsive force between both atoms. The Cl doped a-C film shows consistently the similar results with the N doped a-C film because both N and Cl atoms have large electro-negativity, which causes F atom to push out. If one notes the optimized designing with the suitable doped characteristics, our results could provide a new straightforward strategy to tailor the a-C films with excellent mechanical and other novel physical and chemical properties.

10.
ACS Nano ; 13(10): 12162-12170, 2019 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-31553564

RESUMO

Platinum atomic layers grown on graphene were investigated by atomic resolution transmission electron microscopy (TEM). These TEM images reveal the epitaxial relationship between the atomically thin platinum layers and graphene, with two optimal epitaxies observed. The energetics of these epitaxies influences the grain structure of the platinum film, facilitating grain growth via in-plane rotation and assimilation of neighbor grains, rather than grain coarsening from the movement of grain boundaries. This growth process was enabled due to the availability of several possible low-energy intermediate states for the rotating grains, the Pt-Gr epitaxies, which are minima in surface energy, and coincident site lattice grain boundaries, which are minima in grain boundary energy. Density functional theory calculations reveal a complex interplay of considerations for minimizing the platinum grain energy, with free platinum edges also having an effect on the relative energetics. We thus find that the platinum atomic layer grains undergo significant reorientation to minimize interface energy (via epitaxy), grain boundary energy (via low-energy orientations), and free edge energy. These results will be important for the design of two-dimensional graphene-supported platinum catalysts and obtaining large-area uniform platinum atomic layer films and also provide fundamental experimental insight into the growth of heteroepitaxial thin films.

11.
Sci Rep ; 9(1): 8282, 2019 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-31164674

RESUMO

Highly polarized photoluminescence (PL) from c-plane InGaN/GaN multiple quantum wells (MQWs) grown on stripe-shaped cavity-engineered sapphire substrate (SCES) was realized. The polarization ratio was as high as 0.74 at room temperature. High-resolution X-ray reciprocal space mapping measurements revealed that the InGaN quantum wells on GaN/SCES template were under considerable anisotropic in-plane strain states of -1.178% and -1.921% along the directions perpendicular and parallel to the stripe-pattern, respectively. The anisotropic strain states were attributed to the anisotropic alignment of cavity-incorporated sapphire nano-membranes, which accommodated both anisotropic elastic relaxation in the InGaN quantum well plane as well as the graded elastic relaxation along the vertical direction in the GaN template adjacent to the InGaN/GaN MQWs. The partial strain relaxation in the InGaN wells also contributed to reduction of quantum confined Stark effect, resulting in four times higher PL intensity than InGaN/GaN MQWs on planar sapphire substrate. From theoretical calculations based on k∙p perturbation theory, it was found that fundamental origin of the polarized optical emission was strain-induced modification of valence band structures of the InGaN/GaN MQWs on the SCES. This study will allow us to realize light emitting diodes with highly polarized emission with conventional c-plane sapphire substrates by strain-induced valence band modification.

12.
ACS Nano ; 13(2): 2379-2388, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30673212

RESUMO

We present an atomic level study of reversible cyclization processes in suspended nanoconstricted regions of graphene that form linear carbon chains (LCCs). Before the nanoconstricted region reaches a single linear carbon chain (SLCC), we observe that a double linear carbon chain (DLCC) structure often reverts back to a ribbon of sp2 hybridized oligoacene rings, in a process akin to the Bergman rearrangement. When the length of the DLCC system only consists of ∼5 atoms in each LCC, full recyclization occurs for all atoms present, but for longer DLCCs we find that only single sections of the chain are modified in their bonding hybridization and no full ring closure occurs along the entire DLCCs. This process is observed in real time using aberration-corrected transmission electron microscopy and simulated using density functional theory and tight binding molecular dynamics calculations. These results show that DLCCs are highly sensitive to the adsorption of local gas molecules or surface diffusion impurities and undergo structural modifications.

13.
ACS Appl Mater Interfaces ; 10(48): 41487-41496, 2018 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-30398854

RESUMO

Solid-phase epitaxy (SPE), a solid-state phase transition of materials from an amorphous to a crystalline phase, is a convenient crystal growing technique. In particular, SPE can be used to grow α-Al2O3 epitaxially with a novel structure that provides an effective substrate for improved performance of light-emitting diodes (LEDs). However, the inevitable two-step phase transformation through the γ-Al2O3 phase hinders the expected improved crystallinity of α-Al2O3, and thereby further enhancement of LED performance. Herein, we provide a fundamental understanding of the SPE growth mechanism from amorphous to metastable γ-Al2O3 using transmission electron microscopy (TEM) and density functional theory (DFT) calculations. The nanobeam precession electron diffraction technique enabled clear visualization of the double-positioning domain distribution in the SPE γ-Al2O3 film and emphasized the need for careful selection of the viewing directions for any investigation of double-positioning domains. Void and stacking fault defects further investigated by high-resolution scanning TEM (STEM) analyses revealed how double-positioning domains and other SPE growth behaviors directly influence the crystallinity of SPE films. Additionally, DFT calculations revealed the origins of SPE growth behavior. The double-positioning γ-Al2O3 domains randomly nucleate from the α-Al2O3 substrate regardless of the α-Al2O3 termination layer, but the large energy requirement for reversal of the γ-Al2O3 stacking sequence prevents it from switching the domain type during the crystal growth. We expect that this study will be useful to improve the crystallinity of SPE γ- and α-Al2O3 films.

14.
Nanoscale ; 10(40): 19212-19219, 2018 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-30303224

RESUMO

The recent emergence of vertically stacked van der Waals (vdW) heterostructures provides new opportunities for these materials to be employed in a wide range of novel applications. Understanding the interlayer coupling in the stacking geometries of the heterostructures and its effect on the resultant material properties is particularly important for obtaining materials with desirable properties. Here, we report that the atomic bonding between stacked layers and thereby the interlayer properties of the vdW heterostructures can be well tuned by the substrate surface defects using WS2 flakes directly grown on graphene. We show that the defects of graphene have no significant effect on the crystal structure or the quality of the grown WS2 flakes; however, they have a strong influence on the interlayer interactions between stacked layers, thus affecting the layer deformability, thermal stability, and physical and electrical properties. Our experimental and computational investigations also reveal that WS2 flakes grown on graphene defects form covalent bonds with the underlying graphene via W atomic bridges (i.e., formation of larger overlapping hybrid orbitals), enabling these flakes to exhibit different intrinsic properties, such as higher conductivity and improved contact characteristics than heterostructures that have vdW interactions with graphene. This result emphasizes the importance of understanding the interlayer coupling in the stacking geometries and its correlation effect for designing desirable properties.

15.
Adv Mater ; 30(30): e1707260, 2018 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-29882243

RESUMO

Following the celebrated discovery of graphene, considerable attention has been directed toward the rich spectrum of properties offered by van der Waals crystals. However, studies have been largely limited to their 2D properties due to lack of 1D structures. Here, the growth of high-yield, single-crystalline 1D nanobelts composed of transition metal ditellurides at low temperatures (T ≤ 500 °C) and in short reaction times (t ≤ 10 min) via the use of tellurium-rich eutectic metal alloys is reported. The synthesized semimetallic 1D products are highly pure, stoichiometric, structurally uniform, and free of defects, resulting in high electrical performances. Furthermore, complete compositional tuning of the ternary ditelluride nanobelts is achieved with suppressed phase separation, applicable to the creation of unprecedented low-dimensional materials/devices. This approach may inspire new growth/fabrication strategies of 1D layered nanostructures, which may offer unique properties that are not available in other materials.

16.
Opt Express ; 26(10): A450-A461, 2018 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-29801265

RESUMO

Breaking the total internal reflection far above a critical angle (i.e., outcoupling deep-trap guided modes) can dramatically improve existing light-emitting devices. Here, we report a deep-trap guided modes outcoupler using densely arranged microstructured hollow cavities. Measurements of the leaky mode dispersions of hollow-cavity gratings accurately quantify the wavelength-dependent outcoupling strength above a critical angle, which is progressively improved over the full visible spectrum by increasing the packing density. Comparing hollow- and filled-cavity gratings, which have identical morphologies except for their inner materials (void vs. solid sapphire), reveals the effectiveness of using the hollow-cavity grating to outcouple deep-trap guided modes, which results from its enhanced transmittance at near-horizontal incidence. Scattering analysis shows that the outcoupling characteristics of a cavity array are dictated by the forward scattering characteristics of their individual cavities, suggesting the importance of a rationally designed single cavity. We believe that a hollow-cavity array tailored for different structures and spectra will lead to a technological breakthrough in any type of light-emitting device.

17.
Opt Express ; 26(5): 6249-6259, 2018 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-29529816

RESUMO

In this paper, InAs0.81Sb0.19-based hetero-junction photovoltaic detector (HJPD) with an In0.2Al0.8Sb barrier layer was grown on GaAs substrates. By using technology computer aided design (TCAD), a design of a barrier layer that can achieve nearly zero valance band offsets was accomplished. A high quality InAs0.81Sb0.19 epitaxial layer was obtained with relatively low threading dislocation density (TDD), calculated from a high-resolution X-ray diffraction (XRD) measurement. This layer showed a Hall mobility of 15,000 cm2/V⋅s, which is the highest mobility among InAsSb layers with an Sb composition of around 20% grown on GaAs substrates. Temperature dependence of dark current, photocurrent response and responsivity were measured and analyzed for fabricated HJPD. HJPD showed the clear photocurrent response having a long cutoff wavelength of 5.35 µm at room temperature. It was observed that the dark current of HJPDs is dominated by the diffusion limited current at temperatures ranging from 200K to room temperature from the dark current analysis. Peak responsivity of HJPDs exhibited the 1.18 A/W and 15 mA/W for 83K and a room temperature under zero bias condition even without anti-reflection coating (ARC). From these results, we believe that HJPDs could be an appropriate PD device for future compact and low power dissipation mid-infrared on-chip sensors and imaging devices.

18.
Nano Lett ; 18(2): 1323-1330, 2018 02 14.
Artigo em Inglês | MEDLINE | ID: mdl-29361232

RESUMO

In the present study, we found that α-alumina hollow nanoshell structure can exhibit an ultrahigh fracture strength even though it contains a significant number of nanopores. By systematically performing in situ mechanical testing and finite element simulations, we could measure that the fracture strength of an α-alumina hollow nanoshell structure is about four times higher than that of the conventional bulk size α-alumina. The high fracture strength of the α-alumina hollow nanoshell structure can be explained in terms of conventional fracture mechanics, in that the position and size of the nanopores are the most critical factors determining the fracture strength, even at the nanoscales. More importantly, by deriving a fundamental understanding, we would be able to provide guidelines for the design of reliable ceramic nanostructures for advanced GaN light-emitting diodes (LEDs). To that end, we demonstrated how our ultrastrong α-alumina hollow nanoshell structures could be successfully incorporated into GaN LEDs, thereby greatly improving the luminous efficiency and output power of the LEDs by 2.2 times higher than that of conventional GaN LEDs.

19.
RSC Adv ; 8(38): 21164-21173, 2018 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-35539938

RESUMO

For the development of the future ultrahigh-scale integrated memory devices, a uniform tungsten (W) gate deposition process with good conformal film is essential for improving the conductivity of the W gate, resulting in the enhancement of device performance. As the memory devices are further scaled down, uniform W deposition becomes more difficult because of the experimental limitations of the sub-nanometer scale deposition even with atomic layer deposition (ALD) W processes. Even though it is known that the B2H6 dosing process plays a key role in the deposition of the ALD W layer with low resistivity and in the removal of residual fluorine (F) atoms, the roles of H2 and N2 treatments used in the ALD W process have not yet been reported. To understand the detailed ALD W process, we have investigated the effects of H2 and N2 treatment on TiN surfaces for the B2H6 dosing process using first-principles density functional theory (DFT) calculations. In our DFT calculated results, H2 treatment on the TiN surfaces causes the surfaces to become H-covered TiN surfaces, which results in lowering the reactivity of the B2H6 precursor since the overall reactions of the B2H6 on the H-covered TiN surfaces are energetically less favorable than the TiN surfaces. As a result, an effect of the H2 treatment is to decrease the reactivity of the B2H6 molecule on the TiN surface. However, N2 treatment on the Ti-terminated TiN (111) surface is more likely to make the TiN surface become an N-terminated TiN (111) surface, which results in making a lot of N-terminated TiN (111) surfaces, having a very reactive nature for B2H6 bond dissociation. As a result, the effect of N2 treatment serves as a catalyst to decompose B2H6. From the deep understanding of the effect of H2 and N2 during the B2H6 dosing process, the use of proper gas treatment is required for the improvement of the W nucleation layers.

20.
RSC Adv ; 8(68): 39039-39046, 2018 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-35558318

RESUMO

We investigated the overall ALD reaction mechanism for W deposition on TiN surfaces based on DFT calculation as well as the detailed dissociative reactions of WF6. Our calculated results suggest that the overall reactions of the WF6 on the B-covered TiN surfaces are energetically much more favorable than the one on the TiN surfaces, which means that the high reactivity of WF6 with the B-covered TiN surface is attributed to the presence of B-covered surface made by B2H6 molecules. As a result, an effect of the B2H6 flow serves as a catalyst to decompose WF6 molecules. Two additional reaction processes right after WF6 bond dissociation, such as W substitution and BF3 desorption, were also explored to clearly understand the detailed reactions that can occur by WF6 flow. At the first additional reaction process, W atoms can be substituted into B site and covered on the TiN surfaces due to the stronger bonding nature of W with the TiN surface than B atoms. At the second additional reaction process, remaining atoms, such as B and F, can be easily desorbed as by-product, that is, BF3 because BF3 desorption is an energetically favorable reaction with a low activation energy. Furthermore, we also investigated the effect of H2 post-treatment on W-covered TiN surface in order to remove residual F adatoms, which are known to cause severe problems that extremely degrade the characteristics of memory devices. It was found that both H2 dissociative reaction and HF desorption can occur sufficiently well under somewhat high temperature and H2 ambience, which is confirmed by our DFT results and previously reported experimental results. These results imply that the understanding of the role of gas molecules used for W deposition gives us insight into improving the W ALD process for future memory devices.

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