Isotropic atomic layer etching of GaN using SF₆ plasma and Al(CH₃)₃

GaN is an enabling material for light emitting diodes, advanced radio frequency, and power semiconductor devices. However, fabrication of GaN devices often relies on harsh etch processes, which can leave an etch damage layer, limiting final device performance. In this work, an isotropic atomic layer etching (ALE) process involving SF6 plasma and trimethylaluminium [Al(CH3)3] is presented for the controlled etching of GaN, which reduces oxygen and carbon contamination while smoothing the surface. The ALE chemistry was first examined with density functional theory. A comparison between proposed thermal and plasma-driven reactions is made by implementing Natarajan-Elliott analysis, highlighting that the plasma process is a good candidate for GaN ALE. Saturation was experimentally confirmed for both ALE half-cycles at 150 and 300 °C, with etch rates of 0.31 ± 0.01 and 0.40 ± 0.02 nm/cycle, respectively. Analysis of the films post-ALE shows that the RMS roughness of the films decreases from 2.6 ± 0.1 to 1.9 ± 0.1 nm after 25 nm of etching at 300 °C, in agreement with a previously developed curvature-dependent smoothing model. Taken together, this ALE process enables accurate GaN thickness tuning, surface cleaning, and surface smoothing, allowing for further development of GaN devices.</p

Relation between Reactive Surface Sites and Precursor Choice for Area-Selective Atomic Layer Deposition Using Small Molecule Inhibitors

Implementation of vapor/phase dosing of small molecule inhibitors (SMIs) in advanced atomic layer deposition (ALD) cycles is currently being considered for bottom-up fabrication by area-selective ALD. When SMIs are used, it can be challenging to completely block precursor adsorption due to the inhibitor size and the relatively short vapor/phase exposures. Two strategies for precursor blocking are explored: (i) physically covering precursor adsorption sites, i.e., steric shielding, and (ii) eliminating precursor adsorption sites from the surface, i.e., chemical passivation. In this work, it is determined whether steric shielding is enough for effective precursor blocking during area-selective ALD or whether chemical passivation is required as well. At the same time, we address why some ALD precursors are more difficult to block than others. To this end, the blocking of the Al precursor molecules trimethylaluminum (TMA), dimethylaluminum isopropoxide (DMAI), and tris(dimethylamino)aluminum (TDMAA) was studied by using acetylacetone (Hacac) as inhibitor. It was found that DMAI and TDMAA are more easily blocked than TMA because they adsorb on the same surface sites as Hacac, while TMA is also reactive with other surface sites. This work shows that chemical passivation plays a crucial role for precursor blocking in concert with steric shielding. Moreover, the reactivity of the precursor with the surface groups on the non-growth area dictates the effectiveness of blocking precursor adsorption

Approaches and opportunities for area-selective atomic layer deposition

With conventional semiconductor fabrication based on top-down processing reaching its limits in terms of patterning resolution and alignment, there is increasing interest in the implementation of bottom-up fabrication steps. In this contribution, several approaches for bottom-up processing by area-selective atomic layer deposition (ALD) will be reviewed, and the application possibilities and the main challenges in the field will be discussed

Surface chemistry during Atomic Layer Deposition of Pt studied with vibrational sum-frequency generation

A detailed understanding of the growth of noble metals by atomic layer deposition (ALD) is key for various applications of these materials in catalysis and nanoelectronics. The Pt ALD process using MeCpPtMe3 and O2 gas as reactants serves as a model system for the ALD processes of noble metals in general. The surface chemistry of this process was studied by in situ vibrational broadband sum-frequency generation (BB-SFG) spectroscopy, and the results are placed in the context of a literature overview of the reaction mechanism. The BB-SFG experiments provided direct evidence for the presence of CH3 groups on the Pt surface after precursor chemisorption at 250 °C. Strong evidence was found for the presence of a C=C containing complex (e.g., the form of Cp species) and for partial dehydrogenation of the surface species during the precursor half-cycle. The reaction kinetics of the precursor half-cycle were followed at 250 °C, showing that the C=C coverage saturated before the saturation of CH3. This complex behavior points to the competition of multiple surface reactions, also reflected in the temperature dependence of the reaction mechanism. The CH3 saturation coverage decreased significantly with temperature, while the C=C coverage remained constant after precursor chemisorption on the Pt surface for temperatures from 80 to 300 °C. These SFG results have resulted in a better understanding of the Pt ALD process and also highlight the surface chemistry during thin-film growth as a promising field of study for the BB-SFG community

From the bottom-up: toward area-selective atomic layer deposition with high selectivity

Bottom-up nanofabrication by area-selective atomic layer deposition (ALD) is currently gaining momentum in semiconductor processing, because of the increasing need for eliminating the edge placement errors of top-down processing. Moreover, area-selective ALD offers new opportunities in many other areas such as the synthesis of catalysts with atomic-level control. This Perspective provides an overview of the current developments in the field of area-selective ALD, discusses the challenge of achieving a high selectivity, and provides a vision for how area-selective ALD processes can be improved. A general cause for the loss of selectivity during deposition is that the character of surfaces on which no deposition should take place changes when it is exposed to the ALD chemistry. A solution is to implement correction steps during ALD involving for example surface functionalization or selective etching. This leads to the development of advanced ALD cycles by combining conventional two-step ALD cycles with correction steps in multistep cycle and/or supercycle recipes

Reaction Mechanisms during Atomic Layer Deposition of AlF3Using Al(CH3)3and SF6Plasma

Metal fluorides generally demonstrate a wide band gap and a low refractive index, and they are commonly employed in optics and optoelectronics. Recently, an SF6 plasma was introduced as a novel co-reactant for the atomic layer deposition (ALD) of metal fluorides. In this work, the reaction mechanisms underlying the ALD of fluorides using a fluorine-containing plasma are investigated, considering aluminum fluoride (AlF3) ALD from Al(CH3)3 and an SF6 plasma as a model system. Surface infrared spectroscopy studies indicated that Al(CH3)3 reacts with the surface in a ligand-exchange reaction by accepting F from the AlF3 film and forming CH3 surface groups. It was found that at low deposition temperatures Al(CH3)3 also reacts with HF surface species. These HF species are formed during the SF6 plasma exposure and were detected both at the surface and in the gas phase using infrared spectroscopy and quadrupole mass spectrometry (QMS), respectively. Furthermore, QMS and optical emission spectroscopy (OES) measurements showed that CH4 and CHyF4-y (y ≤ 3) species are the main reaction products during the SF6 plasma exposure. The CH4 release is explained by the reaction of CH3 ligands with HF, while CHyF4-y species originate from the interaction of the SF6 plasma with CH3 ligands. At high temperatures, a transition from AlF3 deposition to Al2O3 etching was observed using infrared spectroscopy. The obtained insights indicate a reaction pathway where F radicals from the SF6 plasma eliminate the CH3 ligands remaining after precursor dosing and where F radicals are simultaneously responsible for the fluorination reaction. The understanding of the reaction mechanisms during AlF3 growth can help in developing ALD processes for other metal fluorides using a fluorine-containing plasma as the co-reactant as well as atomic layer etching (ALE) processes involving surface fluorination

Area-Selective Atomic Layer Deposition of TiN Using Aromatic Inhibitor Molecules for Metal/Dielectric Selectivity

Despite the rapid increase in the number of newly developed processes, area-selective atomic layer deposition (ALD) of nitrides is largely unexplored. ALD of nitrides at low temperature is typically achieved by employing a plasma as the coreactant, which is not compatible with most approaches to area-selective ALD. In this work, a plasma-assisted ALD process for area-selective deposition of TiN was developed, which involves dosing of inhibitor molecules at the start of every ALD cycle. Aromatic molecules were identified as suitable inhibitor molecules for metal/dielectric selectivity because of their strong and selective adsorption on transition metal surfaces. A four-step (i.e., ABCD-type) ALD cycle was developed, which comprises aniline inhibitor (step A) and tetrakis(dimethylamino)titanium precursor (step B) dosing steps, followed by an Ar-H2 plasma exposure (step C), during which a substrate bias is applied in the second half of the plasma exposure (step D). This process was demonstrated to allow for ∼6 nm of selective TiN deposition on SiO2 and Al2O3 areas of a nanoscale pattern with Co and Ru non-growth areas. The TiN deposited using this ABCD-type process is of high quality in terms of resistivity (230 ± 30 μω cm) and impurity levels. This developed strategy for area-selective ALD of TiN can likely be extended to area-selective ALD of other nitrides

Nanoscale Encapsulation of Perovskite Nanocrystal Luminescent Films via Plasma-Enhanced SiO2 Atomic Layer Deposition

Photoluminescence perovskite nanocrystals (NCs) have shown significant potential in optoelectronic applications in view of their narrow band emission with high photoluminescence quantum yields and color tunability. The main obstacle for practical applications is to obtain high durability against an external environment. In this work, a low temperature (50 °C) plasma-enhanced atomic layer deposition (PE-ALD) protection strategy was developed to stabilize CsPbBr3 NCs. Silica was employed as the encapsulation layer because of its excellent light transmission performance and water corrosion resistance. The growth mechanism of inorganic SiO2 via PE-ALD was investigated in detail. The Si precursor bis(diethylamino)silane (BDEAS) reacted with the hydroxyl groups (−OH) and thereby initiated the subsequent silica growth while having minimal influence to the organic ligands and did not cause PL quenching. Subsequently, O2 plasma with high reactivity was used to oxidize the amine ligands of the BDEAS precursor while did not etch the NCs. The obtained CsPbBr3 NCs/SiO2 film exhibited exceptional stability in water, light, and heat as compared to the pristine NC film. Based on this method, a white light-emitting diode with improved operational stability was successfully fabricated, which exhibited a wide color gamut (∼126% of the National Television Standard Committee). Our work successfully demonstrates an efficient protection scheme via the PE-ALD method, which extends the applied range of other materials for stabilization of perovskite NCs through this approach

Equivalent electric circuit model of accurate ion energy control with tailored waveform biasing

For atomic scale plasma processing involving precise, (an)isotropic and selective etching and deposition, it is required to precisely control the energy of the plasma ions. Tailored waveforms have been employed to bias the substrate table to accurately control this ion energy. Recent research has shown that switched-mode power converters can be used to generate this kind of waveform, with the benefit of increased energy efficiency and flexibility compared to the traditionally used linear amplifiers. In this article, an improved equivalent electric circuit model of the plasma reactor is proposed to allow simulation and bias waveform optimization. The equivalent circuit is analysed for different process phases, including the charge, discharge and post-discharge phase. The proposed model is suitable for electric circuit simulation and can be used for predicting the electric waveforms and ion energy distribution. Plasma parameters are required as input for the model, thus an empirical parameter identification method based on the electric measurements of the bias voltage and output current waveforms is introduced. Since these electrical measurements do not interact with the plasma process, the proposed parameter identification method is nonintrusive. Experiments have been carried out, which demonstrate that the proposed model and parameter identification method provide the expected accuracy

Isotropic plasma atomic layer etching of Al2O3 using a fluorine containing plasma and Al(CH3)3

Nanofabrication techniques with atomic level precision are needed for advancement to smaller technology nodes in the semiconductor industry. Thermal atomic layer etching (ALE) is currently being developed to isotropically etch material for future applications. In this Letter, an alternative plasma-based ALE process for isotropic etching of Al2O3 is introduced involving SF6 plasma and trimethylaluminium [TMA, Al(CH3)3] pulses, providing higher etch rates and lower processing temperatures than conventional thermal ALE. This process illustrates that a fluorine-containing plasma can serve as a viable reactant for ALE and that plasmas—besides their conventional use in anisotropic ALE—can be employed for isotropic ALE. In situ spectroscopic ellipsometry measurements confirmed saturation of both SF6 plasma and TMA half-cycles, which results in an etch per cycle (EPC) of 3.160.1A˚ at 260 C. The isotropic nature of the plasma ALE process was demonstrated by transmission electron microscopy analysis of Al2O3-coated 3D trench structures after performing ALE cycles. A mechanism of fluorination by F radicals and ligand exchange reactions involving TMA is proposed for this plasma ALE process based on observations from infrared spectroscopy, which are supported by reactant synergy analysis. This work establishes the benefits that a plasma can deliver for isotropic ALE