Plasma etching of high-k and metal gate materials

Etching characteristics of high-k dielectric materials (HfO₂) and metal electrode materials (Pt, TaN) have been studied in high-density chlorine-containing plasmas at pressures around 10 mTorr. The etching of HfO₂ was performed in BCl₃ without rf biasing, giving an etch rate of about 5 nm/min with a high selectivity of >10 over Si and SiO₂. The etching of Pt and TaN was performed in Ar/O₂ with high rf biasing and in Ar/Cl₂ with low rf biasing, respectively, giving a Pt etch rate of about several tens nm/min and a TaN etch rate of about 200 nm/min with a high selectivity of >8 over HfO₂ and SiO₂. The etched profiles were outwardly tapered for Pt, owing to the redeposition of etch or sputter products on feature sidewalls, while the TaN profiles were almost anisotropic, probably owing to the ion-enhanced etching that occurred.     

Fabrication of epitaxial III-nitride cantilevers on silicon (1 1 1) substrates

The molecular beam epitaxy of AlGaN/GaN epilayers on silicon (1 1 1) using an aluminum nitride buffer layer, and subsequent fabrication of free standing III-nitride cantilevers on Si(1 1 1) has been investigated. Transmission electron microscopy (TEM) of cross-section samples reveals a columnar structure consisting of the hexagonal gallium nitride polytype. Selected area diffraction indicates an epitaxial relationship between the gallium nitride and silicon substrate which is described by GaN[0 0 0 1]//Si[1 1 1] and GaN(1 1 0 0)//Si(1 1 1). Imaging of the electronic structure of an AlGaN/GaN interface has been investigated by mapping the variation in the plasmon frequency using an electron energy loss spectrometer on a dedicated scanning transmission electron microscope. Cantilevers were fabricated using a combination of etching processes. Nitride etch rates during inductively coupled plasma dry etch processing using a Cl₂/Ar plasma etchant were obtained by monitoring the optical reflectivity of the nitride films in situ. A peak GaN etch rate of 250 nm/min was measured, the etch rate was found to be strongly dependent on the d.c. self-bias. Thin beams of GaN having a length of 7 μm and 0.7 μm thickness, were fabricated and mechanically released from Si(1 1 1) substrates using a combination of two dry ICP etch processes, using Cl₂/Ar and CF₄/Ar/O₂ chemistries, and a potassium hydroxide (KOH) aqueous wet etch.     

The dry etching of a sol-gel deposited ZnO thin film in a high density BCl3/Ar plasma

The etching characteristics of zinc oxide (ZnO) including the etch rate and the selectivity of ZnO in a BCl₃/Ar plasma were investigated. It was found that the ZnO etch rate showed a non-monotonic behavior with an increasing BCl₃ fraction in the BCl₃/Ar plasma, along with the RF power, and gas pressure. At a BCl₃ (80%)/Ar (20%) gas mixture, the maximum ZnO etch rate of 50.3 nm/min and the maximum etch selectivity of 0.75 for ZnO/Si were obtained. Plasma diagnostics done with a quadrupole mass spectrometer delivered the data on the ionic species composition in plasma. Due to the relatively high volatility of the by-products formed during the etching by the BCl₃/Ar plasma, ion bombardment in addition to physical sputtering was required to obtain the high ZnO etch rates. The chemical state of the etched surfaces was investigated with X-ray Photoelectron Spectroscopy (XPS). Inferred from this data, it was suggested that the ZnO etch mechanism was due to ion enhanced chemical etching.     

Surface properties of etched ITO thin films using high density plasma

The etching characteristics of ITO in a BCl₃/Ar plasma, including the etch rate and selectivity of ITO, were investigated. The maximum etch rate of 62.8 nm/min for the ITO thin films was obtained at a BCl₃/Ar gas mixing ratio of 25%/75%. Ion bombardment by physical sputtering was required to obtain such high etch rates, due to the relatively low volatility of the by-products formed during the etching. The chemical reactions on the etched surfaces were investigated using X-ray Photoelectron Spectroscopy (XPS) and the preferential losses on the etched surfaces were investigated using Atomic Force Microscopy (AFM).     

Fabrication of epitaxial III-nitride cantilevers on silicon (1 1 1) substrates

The molecular beam epitaxy of AlGaN/GaN epilayers on silicon (1 1 1) using an aluminum nitride buffer layer, and subsequent fabrication of free standing III-nitride cantilevers on Si(1 1 1) has been investigated. Transmission electron microscopy (TEM) of cross-section samples reveals a columnar structure consisting of the hexagonal gallium nitride polytype. Selected area diffraction indicates an epitaxial relationship between the gallium nitride and silicon substrate which is described by GaN[0 0 0 1]//Si[1 1 1] and GaN(1 1 0 0)//Si(1 1 1). Imaging of the electronic structure of an AlGaN/GaN interface has been investigated by mapping the variation in the plasmon frequency using an electron energy loss spectrometer on a dedicated scanning transmission electron microscope. Cantilevers were fabricated using a combination of etching processes. Nitride etch rates during inductively coupled plasma dry etch processing using a Cl₂/Ar plasma etchant were obtained by monitoring the optical reflectivity of the nitride films in situ. A peak GaN etch rate of 250 nm/min was measured, the etch rate was found to be strongly dependent on the d.c. self-bias. Thin beams of GaN having a length of 7 m and 0.7 m thickness, were fabricated and mechanically released from Si(1 1 1) substrates using a combination of two dry ICP etch processes, using Cl₂/Ar and CF₄/Ar/O₂ chemistries, and a potassium hydroxide (KOH) aqueous wet etch.     

HfO2 etching mechanism in inductively-coupled Cl2/Ar plasma

Etching characteristics and the mechanism of HfO₂ thin films in Cl₂/Ar inductively-coupled plasma were investigated. The etch rate of HfO₂ was measured as a function of the Cl₂/Ar mixing ratio in the range of 0 to 100% Ar at a fixed gas pressure (6 mTorr), input power (700 W), and bias power (300 W). We found that an increase in the Ar mixing ratio resulted in a monotonic decrease in the HfO₂ etch rate in the range of 10.3 to 0.7 nm/min while the etch rate of the photoresist increased from 152.1 to 375.0 nm/min for 0 to 100% Ar. To examine the etching mechanism of HfO₂ films, we combined plasma diagnostics using Langmuir probes and quadrupole mass spectrometry with global (zero-dimensional) plasma modeling. We found that the HfO₂ etching process was not controlled by ion-surface interaction kinetics and formally corresponds to the reaction rate-limited etch regime.     

The dry etching property of TiO2 thin films using metal-insulator-metal capacitor in inductively coupled plasma system

In this work, we investigated the etching characteristics of TiO₂ thin films and the selectivity of TiO₂ to SiO₂ in a BCl₃/Ar inductively coupled plasma (ICP) system. The maximum etch rate of 84.68 nm/min was obtained for TiO₂ thin films at a gas mixture ratio of BCl₃/Ar (25:75%). In addition, etch rates were measured as a function of etching parameters, such as the RF power, DC-bias voltage and process pressure. Using the X-ray photoelectron spectroscopy analysis the accumulation of chemical reaction on the etched surface was investigated. Based on these data, the ion-assisted physical sputtering was proposed as the main etch mechanism for the BCl₃-containing plasmas.     

Etch characteristics of HfO2 thin films by using CF4/Ar inductively coupled plasma

In this study, we carried out an investigation of the etching characteristics (etch rate, selectivity) of HfO₂ thin films in the CF₄/Ar inductively coupled plasma (ICP). The maximum etch rate of 54.48 nm/min for HfO₂ thin films was obtained at CF₄/Ar (=20:80%) gas mixing ratio. At the same time, the etch rate was measured as function of the etching parameters such as ICP RF power, DC-bias voltage, and process pressure. The X-ray photoelectron spectroscopy analysis showed an efficient destruction of the oxide bonds by the ion bombardment as well as an accumulation of low volatile reaction products on the etched surface. Based on these data, the chemical reaction was proposed as the main etch mechanism for the CF₄-containing plasmas.     

Reactive ion etching of diamond in CF4, O2, O2 and Ar-based mixtures

The reactive ion etching of diamond in O₂, CF₄/O₂, CHF₃/O₂, O₂/Ar discharges has been examined as a function of bias voltage, flow rate and composition of the gas mixtures. Etching in O₂ and O₂/Ar plasmas (with flow ratio of O₂/Ar 25%) was characterised by a high etch rate (35 nm/min) and an increase in surface roughness with rising bias voltage. The CF₄/O₂ plasmas also produced a high etch rate (50 nm/min) but with only minor dependence of roughness on bias voltage. In comparison, the O₂/Ar (with O₂/Ar flow ratio <25%) and CHF₃/O₂ plasmas resulted in a low etch rate (7–10 nm/min). The high and low rate regimes were identified as ionenhanced chemical etching and physical sputtering respectively. Etching in the O₂/Ar plasmas has been attributed to a combination of the two processes dependent on the O₂ content.     

Texturization of ZnO:Al surface by reactive ion etching in SF<Subscript>6</Subscript>/Ar,CHF<Subscript>3</Subscript>/Ar plasma for application in thin film silicon solar cells

As-deposited sputtered ZnO:Al (AZO) thin films having high transparency (T?≥?85% at 550 nm of wavelength) and good electrical properties (ρ?=?2.59?×?10^?04 Ω cm) are etched to get suitable light trapping in thin film solar cells, using reactive ion etching method in sulfur hexafluoride–argon (SF₆/Ar) plasma and trifluoromethane–argon (CHF₃/Ar) plasma to texture their surface. Though the electrical properties of the films are not affected much by the etching process but significant increment in the average haze values in the wave length range of 350–1100 nm in the etched AZO films (19.21% for SF₆/Ar and 22.07% for CHF₃/Ar plasma etched) are found compared to as-deposited AZO films (5.61%). Increment in haze value is due to more scattering of light from the textured surface. These textured substrates are used as front transparent conducting oxide electrode for the fabrication of amorphous silicon solar cells. Solar cells fabricated on etched AZO substrates show 7.76% increase in conversion efficiency compared to as-deposited AZO substrates.     

Dry etch properties of IZO thin films in a CF4/Ar adaptively coupled plasma system

In this study, we investigated to the etch characteristics of indium zinc oxide (IZO) thin films in a CF₄/Ar plasma, namely, etch rate and selectivity toward SiO₂. A maximum etch rate of 76.6 nm/min was obtained for IZO thin films at a gas mixture ratio of CF₄/Ar (25:75%). In addition, etch rates were measured as a function of etching parameters, including adaptively coupled plasma chamber pressure. X-ray photoelectron spectroscopy analysis showed efficient destruction of the oxide bonds by ion bombardment, as well as accumulation of low volatile reaction products on the surface of the etched IZO thin films. Field emission Auger electron spectroscopy analysis was used to examine the efficiency of ion-stimulated desorption of the reaction products.     

A study on the etch characteristics of HfAlO3 dielectric thin film in Cl2/Ar gas chemistry using inductively coupled plasma system

Thin films of HfAlO₃, a high-k material, were etched using inductively-coupled plasma. The dry etching mechanism of the HfAlO₃ thin film was studied by varying the Cl₂/Ar gas mixing ratio, RF power, direct current bias voltage, and process pressure. The maximum etch rate of the HfAlO₃ thin film was 16.9 nm/min at a C1₂/(C1₂ + Ar) ratio of 80%. Our results showed that the highest etch rate of the HfAlO₃ thin films was achieved by reactive ion etching using Cl radicals, due to the high volatility of the metal-chlorides. Consequently, the increased chemical effect caused an increase in the etch rate of the HfAlO₃ thin film. Surface analysis by x-ray photoelectron spectroscopy showed evidence that Hf, Al and O reacted with Cl and formed nonvolatile metal-oxide compounds and volatile metal-chlorides. This effect may be related to the concurrence of chemical and physical pathways in the ion-assisted chemical reaction.     

Etch characteristics of TiN/Al2O3 thin film by using a Cl2/Ar adaptive coupled plasma

In this study, we carried out an investigation in the etching characteristics of TiN thin films in a C1₂/Ar adaptive coupled plasma. The maximum etch rate of the TiN thin films was 768 nm/min at a gas mixing ratio of C1₂ (75%)/Ar (25%). At the same time, the etch rate was measured as functions of the various etching parameters. The X-ray photoelectron spectroscopy analysis showed the efficient destruction of the oxide bonds by the ion bombardment as well as the accumulation of low volatile reaction products on the etched surface. Field emission Auger electron spectroscopy analysis was used to examine the efficiency of the ion-stimulated desorption of the reaction products.     

Etch characteristics of TiN/Al2O3 thin film by using a Cl2/Ar adaptive coupled plasma

In this study, we carried out an investigation in the etching characteristics of TiN thin films in a C1₂/Ar adaptive coupled plasma. The maximum etch rate of the TiN thin films was 768 nm/min at a gas mixing ratio of C1₂ (75%)/Ar (25%). At the same time, the etch rate was measured as functions of the various etching parameters. The X-ray photoelectron spectroscopy analysis showed the efficient destruction of the oxide bonds by the ion bombardment as well as the accumulation of low volatile reaction products on the etched surface. Field emission Auger electron spectroscopy analysis was used to examine the efficiency of the ion-stimulated desorption of the reaction products.     

Dry etching of AlN films using the plasma generated by fluoride

The plasma produced by the mixture of fluoride and argon (SF₆/Ar) was applied for the dry etching of AlN films. Very high etching rate up to 140 nm/min have been observed. The effects of the bias voltage and the plasma component on the etching results were investigated. It shows that AlN can be effectively etched by the plasma with the moderate SF₆ concentration and the etching rate varies linearly with the bias voltage. The FTIR spectra confirm that AlF₃ is formed due to the chemical reaction of Al and F atoms. The mechanism of AlN etching in F-based plasma is probably a combination between physical sputtering and chemical etching and can be briefly outlined: (i) F⁻ ions reacts with Al atoms to form low volatile product AlF₃ and passivate the surface, and (ii) at the same time the Ar⁺ ions sputter the reaction product from the surface and keep it fluoride free to initiate further reaction. AlF₃ formed on the patterned sidewall play a passivation role during the etching process. The etching process is highly anisotropic with quite smooth surface and vertical sidewalls.     

A study of the surface reaction on the etched ITO thin films by using inductively coupled plasma

In this study, we investigated the etching characteristics of indium tin oxide (ITO) thin films at CF₄/Ar plasma. The maximum etch rate of 29.8 nm/min for the ITO thin films was obtained at CF₄/Ar (=80/20) gas mixing ratio. The standard conditions were the RF power of 800 W, the DC-bias voltage of −150 V, the process pressure of 2 Pa, and the substrate temperature of 40 °C. Corresponding to these etching conditions, chemical reaction of the etched ITO surface has been studied by X-ray photoelectron spectroscopy measurement to investigate the chemical reactions between the surfaces of ITO thin film and etch species. The preferential losses on the etched surfaces were investigated using atomic force microscopy.     

Dry etching characteristics of HfAlO3 thin films in BCl3/Ar plasma using inductively coupled plasma system

In this study, we monitored the HfAlO₃ etch rate and selectivity to SiO₂ as a function of the etch parameters (gas mixing ratio, RF power, DC-bias voltage, and process pressure). A maximum etch rate of 52.6 nm/min was achieved in the 30% BCl₃/(BCl₃ + Ar) plasma. The etch selectivity of HfAlO₃ to SiO₂ reached 1.4. As the RF power and the DC-bias voltage increased, the etch rate of the HfAlO₃ thin film increased. As the process pressure decreased, the etch rate of the HfAlO₃ thin films increased. The chemical state of the etched surfaces was investigated by X-ray Photoelectron Spectroscopy (XPS). According to the results, the etching of HfAlO₃ thin films follows the ion-assisted chemical etching mechanism.     

Etching characteristics and mechanism of Pb(Zr,Ti)O3 thin films in CF4/Ar inductively coupled plasma

The effect of the CF₄/Ar mixing ratio on the etching behaviour and mechanisms for Pb(Zr,Ti)O₃ (PZT) thin films in an inductively coupled plasma was carried out. It was found that an increase of Ar mixing ratio causes non-monotonic behaviour of the PZT etch rate, which reaches a maximum of 2.38 nm/s at 80% Ar. Investigating the plasma parameters, we found a weak sensitivity of both electron temperature and electron density to the change of CF₄/Ar mixing ratio. A combination of zero-dimensional plasma model with the model of surface kinetics shows the possibility of a non-monotonic etch rate behaviour due to the concurrence of physical and chemical pathways in the ion-assisted chemical reaction.     

Etch characteristics of FePt magnetic thin films using inductively coupled plasma reactive ion etching

Etch characteristics of L10 FePt thin films masked with TiN films were investigated using an inductively coupled plasma (ICP) reactive ion etching in a CH₃OH/Ar plasma. As the CH₃OH gas was added to Ar, the etch rates of FePt thin films and TiN hard mask gradually decreased, and the etch profile of FePt films improved with high degree of anisotropy. With increasing ICP rf power and dc-bias voltage to substrate and decreasing gas pressure, the etch rate increased and the etch profile becomes vertical without any redepositions or etch residues. Based on the etch characteristics and surface analysis of the films by X-ray photoelectron spectroscopy, it can be concluded that the etch mechanism of FePt thin films in a CH₃OH/Ar gas does not follow the reactive ion etch mechanism but the chemically assisted sputter etching mechanism, due to the chemical reaction of FePt film with CH₃OH gas.     

Etch characteristics of indium zinc oxide thin films using inductively coupled plasma of a Cl2/Ar gas

Inductively coupled plasma reactive ion etching of indium zinc oxide (IZO) thin films masked with a photoresist was performed using a Cl₂/Ar gas. The etch rate of the IZO thin films increased as Cl₂ gas was added to Ar gas, reaching a maximum at 60% Cl₂ and decreasing thereafter. The degree of anisotropy in the etch profile improved with increasing coil rf power and dc-bias voltage. Changes in pressure had little effect on the etch profile. X-ray photoelectron spectroscopy confirmed the formation of InCl₃ and ZnCl₂ on the etched surface. The surface morphology of the films etched at high Cl₂ concentrations was smoother than that of the films etched at low Cl₂ concentrations. These results suggest that the dry etching of IZO thin films in a Cl₂/Ar gas occurs according to a reactive ion etching mechanism involving ion sputtering and a surface reaction.