Selective Wet Etching Research Articles

(Invited) Selective Wet Etching of Semiconductor Materials by Novel Catalyst-assisted Modes

Since reports in the mid-1990s on metal-induced pitting on a Si surface in microelectronics, much attention has been paid to the positive use of corrosion of a semiconductor surface loaded with a metallic catalyst in solutions, known as metal-assisted chemical etching. This paper describes two novel modes of catalyst-assisted etching. The first involves the formation of nano trenches along the atomic step edges of a Si(111) surface with the help of self-assembled metallic nanowires, enabling the separation of neighboring terraces. The second discusses the science and application of nanocarbon-assisted etching, free from noble metals, of a Ge surface in water.

Microstructural Passivation of Patterned Al2O3 Back Contacts on CdS/CdTe Solar Cells

AbstractPatterned aluminum oxide (Al2O3) back contact on cadmium telluride (CdTe) solar cells can effectively mitigate the loss of the majority carriers while retaining the passivation benefits for minority carriers. This study investigates the impact of the point‐contact geometry on cell performance, where the spacing of the microholes is systematically varied at a constant microhole diameter (≈16 µm). Microhole arrays are created on an evaporated Al2O3 layer (≈30 nm) on CdTe using laser‐beam lithography and selective wet etching processes. Comparative analysis indicates a significant decrease in fill factor (FF) and short‐circuit current (ISC) when the contact fraction falls below 30%, likely due to the Al2O3 barrier impeding majority carriers. Above this fraction, FF and ISC are comparable to those of baseline CdTe cells without Al2O3. Open‐circuit voltage (VOC) shows a gradual decrease as Al2O3 coverage is reduced but exhibits a slight increase (<15 mV) when the contact fraction exceeds 30%. Cathodoluminescence (CL) characterization reveals that significantly improved radiative recombination occurs within the CdTe grain bulk with Al2O3, whereas this effect on grain boundaries is minimal. The findings imply complex local carrier dynamics in the patterned back‐contact region, closely tied to the microstructural properties of CdTe‐based solar cells.

Deposition of CdSe Nanocrystals in Highly Porous SiO2 Matrices-In Situ Growth vs. Infiltration Methods.

Embedding quantum dots into porous matrices is a very beneficial approach for generating hybrid nanostructures with unique properties. In this contribution we explore strategies to dope nanoporous SiO2 thin films made by atomic layer deposition and selective wet chemical etching with precise control over pore size with CdSe quantum dots. Two distinct strategies were employed for quantum dot deposition: in situ growth of CdSe nanocrystals within the porous matrix via successive ionic layer adsorption reaction, and infiltration of pre-synthesized quantum dots. To address the impact of pore size, layers with 10 nm and 30 nm maximum pore diameter were used as the matrix. Our results show that though small pores are potentially accessible for the in situ approach, this strategy lacks controllability over the nanocrystal quality and size distribution. To dope layers with high-quality quantum dots with well-defined size distribution and optical properties, infiltration of preformed quantum dots is much more promising. It was observed that due to higher pore volume, 30 nm porous silica shows higher loading after treatment than the 10 nm porous silica matrix. This can be related to a better accessibility of the pores with higher pore size. The amount of infiltrated quantum dots can be influenced via drop-casting of additional solvents on a pre-drop-casted porous matrix as well as via varying the soaking time of a porous matrix in a quantum dot solution. Luminescent quantum dots deposited via this strategy keep their luminescent properties, and the resulting thin films with immobilized quantum dots are suited for integration into optoelectronic devices.

Wide-range angle sensing based on mixed variable line spacing gratings

Variable line spacing (VLS) gratings are core components in spatial spectrum and synchrotron radiation facilities due to their merits of self-focusing, aberration correction, and flat focal field. However, optimal design and fabrication of VLS gratings are still required for matching various applications. Scratch-induced selective wet etching has been proven as a robust way for fabricating various nanostructures because of its simplicity, flexibility, and controllability. In this paper, we proposed convenient and maskless methods to fabricate VLS grating based on scratch-induced selective wet etching. During the etching, key factors, including normal load for the scratching, etching time, and types of etchants, were investigated systematically toward optimizing the process. The shapes including sidewall angle and the bottom curvature of the grating elements can be controlled by adjusting the normal load, etching time and/or etching etchants. It is found that the VLS gratings present a wide-range sensing for angle detection based on the reflection spectrum. Furthermore, combining transferring process, the VLS master gratings could be replicated on polydimethylsiloxane (PDMS) surface, which showed great optical performance. This work opened new light to some extent for the application of angle sensing and structural color showing.

Coral-shaped AlSi anode materials for Li-ion batteries enabled by THF-based electrolyte

This research aims to implement a strategy of using a controlled acidic etching on AlSi alloy particles to partially remove Al and preserve a porous Si framework as anode materials. The etched AlSi materials with different Al/Si weight ratios have been investigated in lithium-ion batteries. Microstructural analysis shows the evolution of the AlSi material during selective wet etching, highlighting the preservation of coral-shaped Si nanostructures with an Al-rich core. Lower Al/Si ratios result in increased surface area and pore volume, which is favorable for improving lithium-ion diffusion and accommodating volume expansion during cycling. Evaluation of electrochemical performance in different electrolytes proves the importance of electrolyte selection for AlSi anodes. The tetrahydrofuran-based (THF-based) electrolyte stabilizes electrochemical reactions, resulting in superior specific capacity, cycle life, and Coulombic efficiency compared to the carbonate-based electrolyte with fluoroethylene carbonate additive. Rate performance analysis shows excellent high-rate capability with stable capacity retention at 3C, particularly in Al53Si47 and Al10Si90 materials. Electrochemical impedance spectroscopy measurements emphasize the critical role of porous structure and electrolytes in sustaining low resistance and enhancing cycle life performance. Selective aluminum etching and the THF-based electrolyte effectively mitigate the breakdown and subsequent reformation of the solid electrolyte interphase, resulting in superior efficiency and extended lifespan.

Unveiling polycrystalline silicon channel dissolution mechanism in wet etching process of 3D NAND fabrication

3D NAND is one of the most promising storage devices due to its high storage density and low energy consumption. Selective wet etching of Si3N4 by hot-concentrated phosphoric acid (PA) solution is a key process for 3D NAND fabrication. However, the channel material, polycrystalline silicon (poly-Si), is unexpectedly dissolved due to its inevitable exposure to the PA etching solution, which causes device failure and thus limits the stacking density of 3D NAND. Herein, to avoid the detrimental dissolution of poly-Si, we unveil the mechanism of poly-Si dissolution in PA solution from kinetic and thermodynamic perspectives. We find that the etch process shows a two-stage reaction, in which H2O plays a key role in lowering the activation barrier for poly-Si etching. Further thermodynamic analysis demonstrates that poly-Si prefers to be oxidized by H2O to suboxide rather than to SiO2. Combined with surface chemistry characterization, we propose the dissolution mechanism as a two-stage process involving the dissolution of suboxide interface and bulk poly-Si, where the nucleophilic substitution of Si–H with Si–OH on bulk poly-Si surface determines the overall etch rate. This study advances the 3D NAND development by establishing a theoretical foundation for identifying and implementing efficacious strategies to impede detrimental dissolution.

Demonstration of HCl-Based Selective Wet Etching for N-Polar GaN with 42:1 Selectivity to Al0.24Ga0.76N

A wet-etching technique based on a mixture of hydrochloric (HCl) and nitric (HNO3) acids is introduced, demonstrating exceptional 42:1 selectivity for etching N-polar GaN over Al0.24Ga0.76N. In the absence of an AlGaN etch stop layer, the etchant primarily targets N-polar unintentionally doped (UID) GaN, indicating its potential as a suitable replacement for selective dry etches in the fabrication of GaN high-electron-mobility transistors (HEMTs). The efficacy and selectivity of this etchant were confirmed through its application to a gate recess module of a deep-recess HEMT, where, despite a 228% over-etch, the 2.6 nm AlGaN etch stop layer remained intact. We also evaluated the proposed method for the selective etching of the GaN cap in the n+ regrowth process, achieving a contact resistance matching that of a BCl3/SF6 ICP process. These findings underscore the applicability and versatility of the etchant in both the electronic and photonic domains and are particularly applicable to the development of N-polar deep-recess HEMTs.

Single-Crystal Silicon Nanotubes, Hollow Nanocones, and Branched Nanotube Networks.

We report a general approach for the synthesis of single-crystal silicon nanotubes, involving epitaxial deposition of silicon shells on germanium nanowire templates followed by removal of the germanium template by selective wet etching. By exploiting advances in the synthesis of germanium nanowires, we were able to rationally tune the nanotube internal diameters (5-80 nm), wall thicknesses (3-12 nm), and taper angles (0-9°) and additionally demonstrated branched silicon nanotube networks. Field effect transistors fabricated from p-type nanotubes exhibited a strong gate effect, and fluid transport experiments demonstrated that small molecules could be electrophoretically driven through the nanotubes. These results demonstrate the suitability of silicon nanotubes for the design of nanoelectrofluidic devices.

High-temperature annealing of ( ) β-Ga2O3 substrates for reducing structural defects after diamond sawing

A commercial epi-ready ( ) β-Ga2O3 wafer was investigated upon diamond sawing into pieces measuring 2.5 × 3 mm2. The defect structure and crystallinity in the cut samples has been studied by X-ray diffraction and a selective wet etching technique. The density of defects was estimated from the average value of etch pits calculated, including near-edge regions, and was obtained close to 109 cm−2. Blocks with lattice orientation deviated by angles of 1−3 arcmin, as well as non-stoichiometric fractions with a relative strain about (1.0−1.5) × 10−4 in the [ ] direction, were found. Crystal perfection was shown to decrease significantly towards the cutting lines of the samples. To reduce the number of structural defects and increase the crystal perfection of the samples via increasing defect motion mobility, the thermal annealing was employed. Polygonization and formation of a mosaic structure coupled with dislocation wall appearance upon 3 h of annealing at 1100 °C was observed. The fractions characterized by non-stoichiometry phases and the block deviation disappeared. The annealing for 11 h improved the homogeneity and perfection in the crystals. The average density of the etch pits dropped down significantly to 8 × 106 cm−2.

Degradation of Ta2O5 / SiO2 dielectric cavity mirrors in ultra-high vacuum.

In order for optical cavities to enable strong light-matter interactions for quantum metrology, networking, and scalability in quantum computing systems, their mirrors must have minimal losses. However, high-finesse dielectric cavity mirrors can degrade in ultra-high vacuum (UHV), increasing the challenges of upgrading to cavity-coupled quantum systems. We observe the optical degradation of high-finesse dielectric optical cavity mirrors after high-temperature UHV bake in the form of a substantial increase in surface roughness. We provide an explanation of the degradation through atomic force microscopy (AFM), X-ray fluorescence (XRF), selective wet etching, and optical measurements. We find the degradation is explained by oxygen reduction in Ta2O5 followed by growth of tantalum sub-oxide defects with height to width aspect ratios near ten. We discuss the dependence of mirror loss on surface roughness and finally give recommendations to avoid degradation to allow for quick adoption of cavity-coupled systems.

Preventing oxide precipitation in selective wet etching of Si3N4 for 3D-NAND structure fabrication: The role of bubbles

Selective wet etching of Si3N4 is a critical process in the fabrication of 3D-NAND structures; however, it faces a oxide precipitation problem that significantly deteriorates the remaining structure morphology. A recent study by Kim et al.(Kim et al., 2022 [1]) showed that generating CO2 bubbles during the wet etching process efficiently solves the precipitation problem in the fabrication of a 128 multi-layer 3D-NAND structure. In this study, we numerically investigated the multiscale diffusive transport of oxides in the etching process via three different simplified simulations at different scales to reveal the underlying mechanism. We found that mass transport within the multilayer structures alone cannot contribute to the oxide precipitation behavior. Macroscopic transport from the wafer-etchant interface to the bulk must be considered since it contributes to a high oxide concentration at the wafer-etchant surface, which further increases the concentration within the trenches, leading to the precipitation problem. Through the conjecture oxide transport simulation, we found that the large bubbles generated from the reaction agitate the surrounding liquid and dramatically reduce the oxide concentration at the wafer-etchant surface by one order of magnitude, thereby solving the precipitation problem. Our findings clearly explain the experimental results reported by Kim et al. and will further benefit the development of process-intensification technologies in wet etching.

Roles of overlapped scratching in grating fabrications assisted by selective wet etching

Roles of overlapped scratching in grating fabrications assisted by selective wet etching

Extremely high selective Si1−xGex-film wet etchant generating highly dissolved oxygen via peracetic acid oxidant for lateral gate-all-around FETs with a logic node of less than 3-nm

For lateral gate-all-around (LGAA) field-effect transistors (FETs) having design rules of logic devices below 3-nm and 3D-DRAM below 10-nm, multi-stacked Si1−xGex/Si-films should be epitaxially grown on the Si surfaces, and a highly selective wet etching of Si1−xGex-film is essentially followed for forming nanoscale-thick (5–7 nm) Si channel multi-sheets. A high selective etchant has required a lateral Si1−xGex etch rate of >30 nm⋅min-1 and etch rate selectivity between Si1−xGex- and Si-films of >200:1 at patterned multi-stacked Si1−xGex/Si-films. The selective Si1−xGex-film etchant using an etching agent (HF), a selectivity enhancing agent (CH3COOH), and a strong oxidant peracetic acid (PAA; CH3COOOH) unlike a conventional oxidant (H2O2 or HNO3) presented an extremely high Si0.5Ge0.5-film etch rate (82 nm⋅min-1@5 wt% of PAA) and etch rate selectivity between the Si0.5Ge0.5- and Si-films (265:1). Thus, it performed sufficient lateral Si1−xGex-film etching in the 3 multi-stacked Si0.5Ge0.5/Si-films line pattern and satisfied the requirement for a selective etching of Si1−xGex-film for LGAA having a logic-node of less than 2.1-nm. The excellent Si1−xGex-film etch rate using PAA was driven by a lower decomposition energy, lower Gibbs free energy, and higher standard reduction potential compared to the oxidant H2O2. Therefore, the amount of diffused dissolved oxygen using 5 wt% PAA was ∼1.48 times higher than that of H2O2; hence, the chemical oxidation degree (GeOx, and SiOx-bonds on the Si0.5Ge0.5-film surface) for 5 wt% PAA was ∼1.1 times higher than that of H2O2. Furthermore, the etch rate of the Si0.5Ge0.5-film using 5 wt% PAA was ∼5.4 times higher than that of H2O2; thus, we provide a cost effective Si1−xGex-film etching process for LGAA.

Selective Wet and Dry Etching of NiO over β-Ga2O3

In this study, a reaction-limited chemical wet etching process of NiO by an HNO3-based solution, with a complete selectivity over β-Ga2O3 was investigated. The threshold ion energies for inductively coupled plasmas (ICP) dry etching of NiO in BCl3 discharges, its selectivity to β-Ga2O3, and the cleaning effect for chlorine-based residues remaining on the surface after plasma exposure was also examined. One of the major drawbacks of β-Ga2O3 device design is the lack of p-type dopants. An alternative approach is to use a p-type oxide, NiO, to form heterojunctions with n-type Ga2O3. Therefore, a selective wet and dry etching process development is in demand for the optimized pattern transfer process. A solution of 1 HNO3: 4 H2O exhibited measurable etch rates for NiO above 40°C and wet etching activation energy of 172.9 kJ.mol-1 (41.3 kCal.mol-1, 1.8 eV/atom), which is firmly in the reaction-limited regime. The selectivity over β-Ga2O3 was infinite for temperatures up to 55 °C. The strong negative enthalpy for producing the etch product Ga(OH)4 suggests that HNO3-based wet etching of NiO occurs via the formation and dissolution of hydroxides. The BCl3/Ar ICP etching produced maximum etch rates up to 300 Å.min-1 for NiO and 800 Å.min-1 for β-Ga2O3 under moderate plasma power conditions. The selectivity for NiO: Ga2O3 was < 1 under all conditions. The ion energy threshold for the initiation of etching NiO was between 35-60 eV, depending on the plasma power conditions. And its etching mechanism was ion-driven, as determined by the linear dependence between etch rate and the square root of ion energy incident on the surface. By sharp contrast, the etching of Ga2O3 had a stronger chemical component without a well-defined ion energy threshold. After being exposed to BCl3 plasmas, both NiO and Ga2O3 surfaces show chlorine residues, which can both be removed by the standard 1NH4OH: 10H2O or 1HCl: 10H2O solution used for native oxide removal. In addition, according to the location of the Cl 2p3/2 peak in the XPS analysis on the surface, the chlorine particles were ionically bonded. Figure 1

(Invited) Fabrication and Device Performance of 2.7 Kv/2.5A NiO/Ga2O3 Heterojunction Power Rectifiers

In this study, The fabrication of a p-n junction NiO/Ga2O3 rectifier in which we employ a bilayer NiO structure with two different doping levels to achieve both high breakdown voltage and low on-state resistance was described. The band alignment of the NiO to the Ga2O3 was measured. Selective wet and dry etch processes for removing NiO from the underlying Ga2O3 was developed. Finally, the dc and switching performance of the rectifiers was characterized. The maximum breakdown voltage was 2.7 kV for a 1 mm diameter rectifier, with 2.5 A forward current and on/off ratio > 108 over a broad range of switching voltages. The reverse recovery time was limited by the measurement circuit but was < 100 µs. These results show the promise of heterojunction rectifiers based on Ga2O3 for future generations of power switching applications. Figure 1

Investigation of Selective Wet Etching of SiGe Substrates for High-Performance Device Manufacturing

The use of SiGe substrate as a semiconductor material is increasing because of its unique properties. In order to manufacture high-performance devices, it is necessary to develop SiGe selective etching technology. In this study, SiGe epi and oxide substrates with varying germanium percentages (15, 25, and 40 %) were used for the investigation of the selective etching process. As the etchant, APM (1:4:20) solutions were used, and added HF and HCl to confirm the pH effect. The evaluation was conducted while adjusting the pH level. In the case of the SiGe epi substrate, the etching rate was very low at high pH, but the etching rate rapidly increased at a specific pH. And then, the etch rate gradually decreased. On the other hand, the etch rates of the oxide substrate rapidly increased as the pH decreased. To explain the etch rate behavior due to the difference in Ge content and type of substrates, the surface chemistry was measured, and the speciation of the solution was analyzed.

SiC Doping Impact during Conducting AFM under Ambient Atmosphere.

The characterization of silicon carbide (SiC) by specific electrical atomic force microscopy (AFM) modes is highly appreciated for revealing its structure and properties at a nanoscale. However, during the conductive AFM (C-AFM) measurements, the strong electric field that builds up around and below the AFM conductive tip in ambient atmosphere may lead to a direct anodic oxidation of the SiC surface due to the formation of a water nanomeniscus. In this paper, the underlying effects of the anodization are experimentally investigated for SiC multilayers with different doping levels by studying gradual SiC epitaxial-doped layers with nitrogen (N) from 5 × 1017 to 1019 at/cm3. The presence of the water nanomeniscus is probed by the AFM and analyzed with the force-distance curve when a negative bias is applied to the AFM tip. From the water meniscus breakup distance measured without and with polarization, the water meniscus volume is increased by a factor of three under polarization. AFM experimental results are supported by electrostatic modeling to study oxide growth. By taking into account the presence of the water nanomeniscus, the surface oxide layer and the SiC doping level, a 2D-axisymmetric finite element model is developed to calculate the electric field distribution nearby the tip contact and the current distributions at the nanocontact. The results demonstrate that the anodization occurred for the conductive regime in which the current depends strongly to the doping; its threshold value is 7 × 1018 at/cm3 for anodization. Finally, the characterization of a classical planar SiC-MOSFET by C-AFM is examined. Results reveal the local oxidation mechanism of the SiC material at the surface of the MOSFET structure. AFM topographies after successive C-AFM measurements show that the local oxide created by anodization is located on both sides of the MOS channel; these areas are the locations of the highly n-type-doped zones. A selective wet chemical etching confirms that the oxide induced by local anodic oxidation is a SiOCH layer.

(Invited) Fabrication and Device Performance of 2.7 Kv/2.5A NiO/Ga2O3 Heterojunction Power Rectifiers

The fabrication and switching characteristics of large diameter (1mm) Ga2O3 heterojunction rectifiers with bilayers of NiO as the p-type layer are reported. The band alignment shows this is a staggered-gap system. Selective wet and dry etching was developed to allow fabrication of vertical geometry heterojunction rectifiers. A forward current of 2.5 Amperes was achieved, with a reverse breakdown voltage of 2.7 kilovolts. The on/off ratio was above 108 over a broad range of switching voltages, with a measurement-limited reverse recovery time of 100 nanoseconds.

Selective Wet and Dry Etching of NiO over β-Ga2O3

Patterning of NiO/Ga2O3 heterojunctions requires the development of selective wet and dry etch processes. Solutions of 1:4 HNO3 :H2O exhibited measurable etch rates for NiO above 40 °C and activation energy for wet etching of 172.9 kJ.mol-1 (41.3 kCal.mol-1, 1.8 eV/atom), which is firmly in the reaction-limited regime. The selectivity over β-Ga2O3 was infinite for temperatures up to 55°C. The strong negative enthalpy for producing the etch product Ga(OH)4 suggests that HNO3-based wet etching of NiO occurs via the formation and dissolution of hydroxides. For dry etching, Cl2/Ar Inductively Coupled Plasmas produced etch rates for NiO up to 800Å.min-1, with maximum selectivities of < 1 over β-Ga2O3. The ion energy threshold for initiation of the etching of NiO was ~55 eV and the etch mechanism was ion-driven, as determined by the linear dependence of etch rate on the square root of ion energy incident on the surface.

Femtosecond-laser-assisted high-aspect-ratio nanolithography in lithium niobate.

We report the successful fabrication of high-aspect-ratio lithium niobate (LN) nanostructures by using femtosecond-laser-assisted chemical etching. In this technique, a 1 kHz femtosecond laser is first used to induce local modifications inside the LN crystal. Then, selective chemical wet etching is conducted using a buffered oxide etch (BOE) solution. The etching rate in the laser-modified area reaches 2 μm h-1, which is enhanced by a factor of ∼660 in comparison to previous reports without laser irradiation. Such high selectivity in chemical etching helps realize high-performance maskless nanolithography in lithium niobate. In the experiment, we have fabricated high-quality LN nanohole arrays. The nanohole size reaches ∼100 nm and its aspect ratio is above 40 : 1. The minimal period of the LN hole array is 300 nm. Our work paves a way to fabricate LN nano-integrated devices for advanced optic and electronic applications.