Silicon etchants

Acidic silicon etchants are mainly used for two purposes for the delineation of crystal defects, as discussed in Section 2.5, or to remove silicon in an isotropic manner. Isotropic etching adds another degree of freedom to the design of micromechanical structures, because all alkaline etches are anisotropic. Most isotropic etchants for silicon were developed in the early days of silicon crystal technology and exhaustive reviews on this topic are available [Tu3, Rul]. A brief summary is given below. 

Wet silicon etchants, due to their versatility and different behaviors, can be arranged into 3 distinct etching classes ... 

HNA (HF + HNO3 + Acetic Acid) Alkali-OH Comparison of Example Bulk Silicon Etchants EDP TMAH XeFj (ethylene (tetramethyl-diamine ammonium pyrochate- hydroxide) chol) Sp0 Plasma DRIE (Deep Reactive Ion Etch)... 

Silicon dioxide has selectivity to many silicon etchants and therefore is a good mask material for self-aligned etching process. In combination with silicon nitride, multistep etching process of three-dimensional structure is possible. Silicon dioxide is also used to seal microchannels. The insulating property of sihcon dioxide makes it a good coating layer of channels in microfluidics. 

A fonn of anisotropic etching that is of some importance is that of orientation-dependent etching, where one particular crystal face is etched at a faster rate than another crystal face. A connnonly used orientation-dependent wet etch for silicon surfaces is a mixture of KOH in water and isopropanol. At approximately 350 K, this etchant has an etch rate of 0.6 pm min for the Si(lOO) plane, 0.1 pm min for the Si(l 10) plane and 0.006 pm miiG for the Si(l 11) plane [24]. These different etch rates can be exploited to yield anisotropically etched surfaces. 

Dry etching is a commonly used teclmique for creating highly anisotropic, patterned surfaces. The interaction of gas phase etchants with surfaces is of fundamental interest to understanding such phenomena as undercutting and the dependence of etch rate on surface structure. Many surface science studies aim to understand these interactions at an atomic level, and the next section will explore what is known about the etching of silicon surfaces. 

On the atomic level, etching is composed of several steps diflfiision of the etch molecules to the surface, adsorption to the surface, subsequent reaction with the surface and, finally, removal of the reaction products. The third step, that of reaction between the etchant and the surface, is of considerable interest to the understanding of surface reactions on an atomic scale. In recent years, STM has given considerable insight into the nature of etching reactions at surfaces. The following discussion will focus on the etching of silicon surfaces [28]. 

The combination of a positive charge and reducibility of tetrazolium salts finds use as anticorrosion agents for metals.634,635 The y are components of an oxidant/etchant bath composition for silicon dioxide corrosion-resistant surfaces.636 They are also used as antistatic agents in polyamide... 

In the early days of silicon device manufacturing the need for surfaces with a low defect density led to the development of CP solutions. Defect etchants were developed at the same time in order to study the crystal quality for different crystal growth processes. The improvement of the growth methods and the introduction of chemo-mechanical polishing methods led to defect-free single crystals with optically flat surfaces of superior electronic properties. This reduced the interest in CP and defect delineation. 

The high selectivity of wet etchants for different materials, e.g. Al, Si, SiOz and Si3N4, is indispensable in semiconductor manufacturing today. The combination of photolithographic patterning and anisotropic as well as isotropic etching of silicon led to a multitude of applications in the fabrication of microelectromechanical systems (MEMS). 

The morphology of alkaline-etched (100) and (110) silicon surfaces varies from rough surfaces that exhibit micron-sized pyramids or ridges [Sc5] to smooth orange peel-like surfaces, depending on the etchant composition and substrate doping density. Mirror-like surfaces can be obtained on (111) crystal planes. 

Masking is required for many micromechanical applications. While Si3N4 is only suitable for a small etching depth because of its significant etch rate in HF, noble metals like gold are sufficient mask materials. In contrast to alkaline etchants, organic materials like certain resists or even some adhesive tapes are well suited to protect the silicon surface in isotropic etchants. 

Etchants for defect and junction delineation are usually composed of HF and an oxidizing agent such as HN03 [Dal, Gr4, Ka4, Nel], K2Cr207 [Se5] or Cr03 [Sil, Jel, Sc7, Ya4, Me5]. Alkaline solutions are rarely used for defect delineation [Mal2], An etch pit will form on a silicon surface if the dissolution rate is enhanced locally. Enhancement of the etch rate may occur for various reasons ... 

Etch pit formation as a result of the factors given in 1-4 above can be used to characterize silicon materials. A summary of common defect etchants for silicon is given in Table 2.1. 

Tab. 2.1 Composition and etch rates of common defect etchants for silicon. ...

In the frame of this model the anisotropy of alkaline etchants, the low etch rate observed for (111) oriented silicon surfaces, can be interpreted as an insufficient polarization of three silicon backbonds by only one Si-OH surface bond that can... 

A prerequisite for all etch-stop techniques discussed so far is an electrical connection to an external power supply. However, if the potential required for passivation in alkaline solutions is below 1 V, it can be generated by an internal galvanic cell, for example by a gold-silicon element [As4, Xil]. An internal galvanic cell can also be realized by a p-n junction illuminated in the etchant, as discussed in the next section. Internal cells eliminate the need for external contacts and make this technique suitable for simple batch fabrication. 

The growth of a macropore on a p-type substrate can be initiated by artificial etch pits. The growth of predefined pore arrays is observed to be more stable than the growth of random pores on flat electrodes [Chl6, Le21]. If a slit is used for pore initiation the formation of trenches separated by thin walls has been observed on (100) p-type substrates [Oh5]. Note that for slits along the (110) direction the walls become (110) planes, in contrast to trenches produced by alkaline etchants, for which only (111) oriented walls can be formed on (110) oriented silicon substrates. 

Microporous silicon is suitable for sacrificial layer applications because of its high etch rate ratio to bulk silicon, because it can be formed selectively, and because of the low temperatures required for oxidation. PS can be formed selectively if the substrate shows differently doped areas, as discussed in Section 4.5, or if a masking layer is used. Noble metal films can be used for masking as well as Si02, Si3N4 and SiC. Oxidation conditions are given in Section 7.6, while the etch rates of an etchant selective to PS are given in Fig. 2.5 b. 

---