Search

In this atomic-scale study on technologically relevant group IV semiconductors, Ge and SiGe, we relate surface chemistry, in particular the nature of surface oxides, to wet etching kinetics. ICP-MS quantification of Ge in HCl solution containing H2O­2 as the oxidizing agent showed that the Si bulk concentration strongly impacted the etching kinetics. Post operando synchrotron XPS provided insight into the surface oxide chemistry involved in the etching process: a non-homogeneous porous layer with a depletion of Ge components at the outer surface due to pull out effects.

Accurate characterization of the underwater stability of superhydrophobic surfaces is crucial for the design of durable anti-fouling materials and advanced microfluidic concepts. Although superhydrophobic breakdown is a major issue that hampers full exploitation of superhydrophobic functional materials, suitable characterization methods are lacking and relatively little is known about the wetting dynamics. In this work we explore a novel method based on attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) for large-area in-situ analysis of wetting states and wetting transitions on nanostructured surfaces. Spontaneous wetting is induced on superhydrophobic silicon nanopillars through in-situ modulation of the liquid composition and surface tension. The high surface sensitivity of ATR-FTIR enables quantitative evaluation of the instantaneous liquid composition and wetted area. Critical transition criteria for superhydrophobic breakdown are assessed using both ATR-FTIR and goniometric measurements. Significant deviations from classical wetting models are revealed, emphasizing the need for more accurate transition criteria and careful experimental validation. Breakdown kinetics near the critical transition are found to be significantly slowed down on nanostructured surfaces, which underlines the necessity for accurate characterization of wetting dynamics at the nanoscale. The proposed ATR-FTIR method can be promising for dynamic studies of wetting transitions on more advanced surfaces, as hierarchical structures or oleophobic designs.

We report on the (electro) chemical etching behavior, surface morphology and composition of n-type Ge (100) in acidic halide solutions using various analytical and spectroscopic techniques. The use of an integrated (electro) chemical etching chamber connected to X-ray photoelectron spectroscopy instrument to exclude the effect of oxygen from atmosphere is highlighted.

The introduction of 3-D nanostructures in semiconductor manufacturing may create wetting issues in aqueous processing. In this work we evaluated the use of a CO2 gas atmosphere to promote the wetting of superhydrophobic nanopillars, relying on the high solubility of CO2 in aqueous solutions. The patterned surface was first flushed with CO2 gas, before dispensing the aqueous solution that was saturated with N2 and switching the gas flow from CO2 to N2. The liquid penetration was characterized by monitoring the disappearance of CO2 gas using ATR-FTIR. Results showed only a modest improvement in wetting, presumably due to a fast N2-CO2 gas exchange at the wetting front.

This work focuses on capillary-induced collapse of high-aspect-ratio silicon nanopillars. Modification of the surface chemistry is demonstrated to be an efficient approach for reducing capillary forces and consequently reduce pattern collapse. Special effort is spent on determination of the wetting state of chemically modified surfaces as complete structure wetting is of utmost importance in wet processing. In light of this, an ATR-FTIR based method has been developed to unambiguously distinguish between wetting and non-wetting states.

Epitaxial growth requires a clean starting surface for the growth of a high-quality crystalline layer. For epitaxy on Si, an HF-last wet clean followed by an in-situ high-temperature hydrogen bake is the reference pre-epi clean sequence to obtain an oxygen-free surface [1, 2]. The temperature required to remove all residual oxygen also makes the surface atoms mobile, resulting in reflow. The high temperatures used during the H2-bake can also result in intolerable doping profile changes. A lower temperature pre-epi clean sequence is required to avoid this reflow, especially when moving away from Si. In addition the high temperatures needed during a H2-bake would result in the relaxation of high mobility channels, e.g. strained Si1-xGex or III-V materials [3]. Several low temperatures pre-epi cleaning solutions have been proposed in the past, e.g. GeH4-assisted H2-bake [4] or more recently, a GeH4-assisted HCl clean [5]. In this study we looked at the interaction between HF-last wet clean and the in-situ GeH4-assisted HCl clean prior to Si0.8Ge0.2-on-Si epitaxy.

Recent studies have shown that even inherently hydrophilic surfaces (θ < 90 ̊) can become hydrophobic as a consequence of nanopatterning (1-4). This creates an issue in semiconductor manufacturing as aqueous chemistries (e.g. dilute HF solutions) are preferred to organic chemistries for their lower cost of ownership and greener environmental profile.

The wet cleaning process plays an important role in advanced semiconductor industry. Particularly when bare silicon areas are exposed, wafer drying can result in undesired watermark (WM) residues on the surface [1-2]. In principle there are three components effecting the formation, shape and size of WM. 1) composition of the ambient like oxygen concentration, relative humidity and temperature affect WM formation [3]. 2) liquid: factors such as pH and the amount of dissolved species inside the liquid influence the WM composition. 3) substrate: for silicon for instance: surface passivation is important for WM formation [2]. WMs are composed of silica that is formed during the drying process by oxidation of the silicon surface [1]. Therefore when studying WM formation it is important to understand the mechanism (s) of silicon oxidation and the dissolution.

of high mobility channels materials like Ge. The introduction of Ge as channel material has already shown significant interests in term of device performance enhancement [1,2]. However, the use of Ge in CMOS integration has raised new challenges in terms of clean or wet etch steps since significant Ge loss occurs when it oxidizes in aqueous media.

The cumulative installed solar power generation has been rising exponentially over the past decade. This has lead to a concomitant rise in production capabilities, leading eventually to excess production capabilities and rapid price declines per unit. In order to compete with the standard electricity generation the cost of solar panel production and installation needs to decrease even further. At the same time the solar panel and cell makers need to be able to keep a healthy margin. A crucial element in this exercise is a close control on the Cost of Ownership (CoO) of a solar cell / panel fabrication site.

The continuous miniaturization of electronic building blocks in the semiconductor industry imposes more stringent requirements on the different cleaning processes. Purely chemical particle cleaning is based on weak etching of the substrate. This etching reduces the attractive van de Waals interaction between particle and substrate and at the same time, electrostatic repulsion ensures the removal of particles. This technique is not applicable anymore for future technology nodes, since an unacceptable large substrate loss (up to 3 nm) is necessary to obtain high particle removal efficiencies with pure chemical cleaning alone [. As a result, an additional physical force has to be considered to overcome this limitation. Several physical cleaning techniques exist, but all of them suffer from too much damage creation when fragile structures are cleaned. Currently, the industry is more focusing on spray cleaning and state-of-the-art spray tools show a high control over droplet size and droplet velocity [2]. Despite all of the advancements in spray cleaning, damage creation of fragile elements remains an issue, which could partially be attributed to the chaotic behavior of the water layer on the wafer surface [3]. Therefore, megasonic cleaning is still considered as a possible alternative to reduce damage formation during a physical cleaning process. Recently, it has been shown that the acoustic pressure amplitude can be reduced while maintaining the same particle removal efficiency level. This is achieved by (1) using pulsed acoustic fields which makes it possible to control the average bubble size and maximize the number of resonant bubbles, by (2) increasing the dissolved gas concentration which facilitates bubble nucleation and, finally, by (3) introducing traveling waves to transport bubbles to the wafer surface which needs to be cleaned. These conditions are briefly discussed and are applied during the investigation of the influence of dissolved CO2 on bubble activity. Dissolved CO2 is particularly interesting since it has been reported that sonoluminescence (i.e. strong bubble collapse) as well as damage formation is reduced when CO2 is added to the cleaning liquid [4,5]. Here, it is shown that also particle removal efficiencies (PREs) diminish with increasing CO2 concentrations.

3D stacked IC (3D-SIC) is one of the main approaches within 3D technologies as it is the most mature and economically viable technology and provides the highest through silicon via density. Enabling 3D SIC requires the modification of standard IC process flows by adding several process modules, such as through silicon via (TSV), wafer bonding and thinning, prior backside processing (e.g. Cu nails exposure), micro bumps formation for the front side and/or the backside and finally stacking to another chips [. Within the 3D-SIC technology developed at IMEC, surface control and preparation by means of wet clean and wet etch are essential steps notably in two key process modules: wafer thinning and micro bump formation.

Removal of particulate residues represents a very challenging step in current CMOS-technology nodes. The continued miniaturization and the introduction of novel materials in the semiconductor industry have resulted in very stringent requirements for device fabrication steps such as cleaning processes [. Physical forces, acting directly on the surface to be cleaned, are currently employed for delicate particle removal as an alternative to more aggressive chemistries [2]. High frequency ultrasounds (500 kHz 4 MHz), or megasonics, rely on the action of oscillating bubbles created during the ultrasonic agitation of the cleaning liquid. Strongly oscillating gas bubbles are able to generate shear forces, which are considered to be responsible for cleaning [3]. However, collapsing bubbles close to a surface can also produce water jets and shockwaves which lead to damage of fragile structures. Fundamental research is needed in order to overcome these issues by improving the understanding of the physical parameters playing a role in the acoustic cavitation of bubbles. This study reports the effects of lowering the surface tension of the liquid bulk on the bubble activity in the MHz range. A lower surface tension (45 mN/m) with respect to water (72 mN/m) is obtained by adding a non-ionic surface-active agent (TritonX-100). After fully characterizing its wettability, a cleaning solution containing surfactant is investigated under pulsed and continuous acoustic fields, for different acoustic amplitudes and gas concentrations. The aim is to increase bubble activity while reducing the strength of the bubble collapse. The results obtained can be useful in tuning megasonic cleaning systems towards more efficient processes.

The industry has diverged into two main approaches for high-k and metal gate (HKMG) integration. One is the so called gate-first. The other is gate-last, also called replacement metal gate (RMG) where the gate electrode is deposited after junctions formation and the high-k gate dielectric is deposited in the beginning of the flow (high-k first-RMG) or just prior to gate electrode deposition (high-k last-RMG) [1-. We can distinguish two RMG process flows called either high-k first or high-k last. In RMG high-k first, poly silicon is removed on top of a TiN etch stop layer whereas on high-k last poly silicon is removed on top of a dummy oxide layer. This dummy oxide has also to be removed in order to redeposit a novel high-k and work function metal (Figure 1).

Atomic force microscope (AFM) with inclined sample measurement and hydrophobic functionalized AFM probe was used to visualize the sidewall of low-k pattern and allowed to characterize the hydrophobic characteristics on the sidewall after low-k etch. To functionalized the AFM probe, 1H,1H,2H,2H-Perfluorodecyltrichlorosilane (FDTS) as a hydrophobic film was coated on an AFM probe. Because of the magnitude of the phobic-phobic interaction force and the tip forced to make a phase shift. Using this technique the visualization and characterization of the etch residue on the low-k sidewall can be successfully performed. It is shown that the investigation toward an effective chemical clean for the etch residue removal could be applicable.

An important problem in megasonic cleaning is the nucleation process of bubbles, which act as the cleaning agents. A fundamental understanding of this nucleation process will help to optimize the cleaning parameters for future applications to achieve damage free cleaning. In this work, we use quantitative stroboscopic Schlieren imaging to study the interaction of nucleating bubbles with a travelling acoustic wave. The advantage of this method is that it is non-interfering, meaning that it does not disturb the bubble nucleation. It is revealed that nucleation mechanism is a 2 step process, where a regime of slow bubble growth due to rectified diffusion is subsequently followed by a transient cavitation cycle, where bubbles grow explosively. The latter is accompanied by broadband acoustic emission and enhanced thermal dissipation, leading to the occurrence of thermal convection visible in the Schlieren images.

The megasonic cleaning efficiency is evaluated as a function of the angle of incidence of acoustic waves on a Si wafer. Acoustic Schlichting streaming alone is not able to remove nanoparticles smaller than 400 nm. It is shown that oscillating or collapsing behavior of bubbles are responsible for removing nanoparticles smaller than 400 nm during a cleaning process with ultrasound. Optimal particle removal efficiency is obtained around the angle of acoustic transmission of the silicon wafer.

An improved fundamental understanding of the megasonic cleaning process is necessary to optimize cleaning efficiency and minimize the unwanted damage to fragile structures. Argon sonoluminescence (SL) measurements are done to achieve an improved insight in the collapse threshold and behavior of microbubbles. This paper reports on acoustic cavitation by means of Ar Sonoluminescence (SL) investigation achieved with a dedicated test cell, a photomultiplier tube (PMT) and a gasification system. The results show an increase in SL signal as a function of the applied acoustic power density. An increase in Ar concentration results in a decrease in SL signal. Furthermore, a clear hysteretic behavior in the SL signal is identified when ramping the acoustic power up and down. This hysteresis effect can be attributed to the nucleation of bubbles during the increasing branch of the power loop. Finally the time evolution of SL light after the switching on of the acoustic transducers revealed the existence of a delay time.

Four different types of FINs; amorphous Si (a-Si), annealed a-Si, polycrystalline Si (poly-Si) and crystalline Si (c-Si) were used to investigate the effect of interfacial strength and the length of structures on the physical cleaning window by measuring their collapse forces by atomic force microscope (AFM). A transmission electron microscope (TEM) and a nanoneedle with a nanomanipulator in a scanning electron microscope (SEM) were employed in order to explain the different collapse behavior and their forces. Different fracture shapes and collapse forces of FINs could explain the influence of the interfacial strength on the pattern strength. Furthermore, the different lengths of a-Si FINs were prepared and their collapse forces were measured and the shorter length reduced their pattern strength. Strong adhesion at the interface resulted in a wider process window while smaller dimensions made the process window narrower.

We report in this work some process optimization effort in performing poly silicon removal for replacement gate process integration. Successful wet poly silicon removal after dummy gate patterning is not only conditioned by suitable process conditions during wet removal but is also impacted by process steps prior to gate removal A thorough evaluation of the impact on poly removal from dopants or contaminants introduced in the poly silicon by previous processing is done, resulting in an optimized integration flow with successful poly removal. This work also shows that use of diluted TMAH chemistry instead of diluted ammonia in performing poly silicon removal provides better ability in removing poly silicon especially in narrow gate structures.

Following Moores scaling law, the transistor source and drain area become shallower and higher doped regions. As a consequence the limitations of substrate and dopant loss during cleaning become more stringent. For a better understanding, highly B, As and P doped blanket substrates, either prepared by ion implantation or by EPI growth, are studied. Substrate and dopant loss as a function of time and different HF etching conditions is monitored by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and additional techniques like Spectroscopic Ellipsometry (SE), .... It is shown that in general, the Si etching is dependent of the position of the Fermi level. More remarkably, the junction (4 nm) of a non-annealed heavily As or P doped substrate is completely removed after less than 20 min of etching in HF. This process is related to enhanced etch rates because of the amorphization of the substrate.

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Not Available

Compound semiconductors based on group III and V elements of the periodic system have high charge carrier mobility and are, therefore, candidates for channel material in future CMOS devices [1]. In order to design wet chemical solutions that lead to appropriate surface pre-conditioning and allow for nanoscale processing and minimal substrate loss, a thorough understanding of the interactions between the substrate and the chemical solutions is needed and the basic etching mechanisms needs to be resolved. The focus of this research is on InP in acidic solutions. ESH aspects are also considered.