To overcome problems in their daily use, a variety of dry electrodes have been proposed. Dry electrodes are those that do not use any liquid conductive medium between the skin and electrode surface. However, in fact, the electrode is not completely dry; there will be some sweat as electrolytes during use. Additionally, depending on the contact methods with the scalp, there are three kinds of dry electrodes: MEMS electrodes, non-contact electrodes, and ordinary-contact electrodes.
2.3.1. MEMS Dry Electrodes
MEMS electrodes are different from the invasive electrodes mentioned in Part 1. The microneedles of MEMS dry electrodes only puncture the stratum corneum, which is composed of dead cells and does not harm brain tissue. From the equivalent circuits, it is very clear that the MEMS dry electrodes avoid the impedance caused by the stratum corneum. Furthermore, since the pin directly pierces the scalp, electrodes will be better fixed, basically avoiding the generation of motion artifacts.
The bioelectric signal quality obtained by MEMS is better compared to other dry electrodes, and the electrochemical noise is lower [
67]. In addition, this method eliminates the need for skin treatment and avoids the tedious preparation steps. There are main three types of microneedle array dry electrodes, including silicon substrate microneedle array dry electrodes, metal microneedle array dry electrodes, and polymer microneedle array electrodes.
The silicon processing technique was initially proposed a long time ago, and now there are three main preparation methods by which to fabricate EEG MEMS electrode substrates [
68,
69,
70,
71,
72,
73], including self-stop etching of doped silicon, deep reactive ion etching, and isotropic and anisotropic reactive ion etching. After the etching, conductive materials are needed for the signal recording. Some metal particles, such as Ti/Pt [
70], Ti/Ag [
72], and Ag/AgCl [
73], are distributed on the substrate by electrodeposition or other surface treatments. Although the manufacturing process of silicon is very mature, it has poor biocompatibility, and microneedles are brittle, which makes them easily break when they penetrate the skin. The application of silicon is thus limited.
In addition to silicon-based microneedle array dry electrodes, there are metal microneedle array dry electrodes and polymer microneedle array dry electrodes, both of which have their own advantages and disadvantages. Metal materials have good mechanical properties and electrical conductivity, so they can penetrate the cuticle better than polymer materials. Metal microneedle array electrodes materials mainly include Ti/Au [
74], Cu [
75,
76], stainless steel [
77], and IrO
2 [
78] as their composition can effectively record bioelectric signals. These materials all have good biocompatibility and are easily obtained. However, there are still some problems with metal microneedle array electrodes. The rigid substrate makes it difficult to come into close contact with the skin, so the comfort level will be poor, and the bad contact will cause unstable signals. The processing technology is still not perfect, which leads to low processing accuracy. Polymer microneedle array dry electrodes have the characteristics of good biocompatibility and low cost. Polymers that are used to prepare microneedle array dry electrodes include PDMS, SU-8, parylene C, epoxy resin, polymethyl methacrylate, and polyimide [
60,
79,
80,
81,
82,
83,
84,
85]. The surface of the polymer microneedles prepared from the above materials also needs to ensure electrode conduction through surface deposition and electroplating metal materials including Au Ag Pt, and Ni, etc. However, polymer microneedle array dry electrodes also have some disadvantages. The polymer has a low hardness, and it cannot easily penetrate the stratum corneum.
At present, a commonly used method is to combine the flexible substrates and the hard microneedle array. This method can not only ensure that the dry electrode can be close to the scalp but also allows the microneedle to penetrate the stratum corneum smoothly. The manufacturing process of microneedle array dry electrodes is becoming increasingly sophisticated, and its application in bioelectrical signal acquisition is gradually increasing, but this electrode does not have the features of being lightweight or integrated at present. In addition, the microneedle piercing the skin will still make users uncomfortable and can cause a risk of infection. As shown in Figure 6, no matter what kind of MEMS electrode, it will have a very sharp structure. With the continuous application of new materials and the constant improvement of the structure, microneedle array dry electrodes will be a good choice for BCI to collect electrical signals.
Figure 6. Typical MEMS electrodes and capacitive electrodes. (
a,
b) Silicon-based microneedle array dry electrodes [
68,
70]. (
c) Metal microneedle array electrodes [
74]. (
d) Polymer-based microneedle array dry electrode [
81].
2.3.2. Non-Contacted Electrodes
Non-contacted electrodes are similar to capacitive coupling directly to the skin, which can collect bioelectric signals without touching the skin. Therefore, they are also called capacitive electrodes. Because of the non-contact performance, capacitive electrodes can overcome the defect of other electrodes that are only able to be used on hairless sites.
Non-contact electrodes contain a metal plate electrode and an active circuit. The active circuit must provide an ultra-high input impedance to avoid signal attenuation because the metal electrode can be viewed as an ultra-small capacitor. The input impedance of the amplifier should reach a high level that is four orders of magnitude greater than that of traditional wet electrodes. As a result, this places high demands on the amplifier. Lee et al. [
86] designed a capacitive electrode composed of upper and lower PDMS layers, a shield plate, an electrode plate, and an adhesive PDMS layer. The electrode plate was fabricated in five layers: 30 μm polyimide, 30 nm titanium, 10 μm Cu, 30 μm Ni, and 100 nm Au. Additionally, the electrode plate was sandwiched by the PDMS layers. In the eye-closed and eye-open tests, the alpha rhythm had correlations of 0.91 and 0.83 with conventional electrodes. Liu et al. [
87] designed a non-contact signal acquisition system with a diameter of 25 mm and made of a flexible printed circuit. The electrode had a two-layer structure. The bottom layer was composed of a copper-filled capacitive sensing plate and a shielding ring to avoid external interferences. The top layer was made of Cu and connected with the outer ring to improve the shielding outcomes. The electrical components were placed on the flexible printed circuit board instead of the back of the non-contact electrode to ensure optimal coupling and comfort. In general, non-contact electrodes cannot be fixed completely, which results in serious motion artifacts. In this regard, Chen et al. [
88] proposed a non-contact electrode containing an active circuit and a metal plate made of Cu. The thickness and diameter were 2 mm and 20 mm, respectively. In addition, the dry electrode had an adaptive mechanical design so that the influence of motion artifacts could be reduced greatly.
In addition, some researchers have made some improvements regarding lightweight designs. Alireza et al. [
89] proposed a wearable wireless device for EEG monitoring and analysis. The substrate was made of a four-layer polyimide on which the recording, quantization, and motion artifact removal circuitries were implemented. The whole wearable solution with the battery weighed 9.2 g. Due to its lightweight design, the electrode could not only be used in a laboratory but also for ambulatory EEG recording. The eight channels were sufficient to ensure that brain neural activity could be recorded with a reasonable spatial resolution.
From the above references, there is no doubt that copper is a commonly used capacitor material because of its accessibility, good molding property, and good conductivity. The electrode does not require a strict performance for materials. Compared to wet electrodes, the correlation between the two electrodes is about 90% and can meet the basic requirements for application. In addition, from Alireza’s work [
89], non-contracted electrodes had the characteristic of being lightweight (9.2 g). The biggest obstacle to the development of capacitive electrodes is the motion artifact caused by the high impedance and phase shift [
90].
2.3.3. Common-Contact Dry Electrodes
Common-contact dry electrodes are the most convenient type since they can directly contact the scalp, but do not penetrate the cuticle or require skin pre-treatment. The existence of hair will hinder the good contact between the electrode and the scalp, which usually requires some special structures for the electrodes to make themselves pass through the hair, such as being finger shaped. For the sake of comfort and high geometric conformity between the sensor and the irregular scalp surface, there is always a spring structure at the end of the probe to cushion the pressure on the scalp. Metal with good conductivity and biocompatibility is usually used for this special structure.
As described by Liao et al. [
66] in this article, BeCu was used as the electrode column, and Au with good biocompatibility was attached to the contact area between the electrode column and the scalp. A total of 17 probes were next inserted into the thin Cu plate that served as the flexible substrate of the sensor (
Figure 7a). Therefore, a good EEG signal can be obtained without skin preparation. Similarly, Liu et al. [
91] proposed a spring-type electrode, in which a platinum nanoporous layer was attached to six probes of the electrode so as to decrease contact impedance and enhance conductivity (
Figure 7b). Finally, the contact impedance of the dry EEG sensors, which were attached to the different sites, was below 20 kΩ. In the resting-state EEG measurement, the correlations compared to wet electrodes ranged from 0.8179 to 0.9677. Furthermore, coating conductive materials on polymer surfaces can take advantage of the softness of polymer and avoid the use of complex spring structures. Fiedler et al. [
92] deposited a conductive TiN layer on a polyurethane (PU) substrate by using a multiphase DC magnetron sputtering technique (
Figure 7c). Thus, the electrode was able to fit the shape of the brain and keep good contact with it. The electrode had a specific structure with 36 electrode pins on a single baseplate. Compared to wet electrodes, the variance of both signals was in the same order of magnitude. In addition, finger-shaped electrodes can be obtained by 3D printing. After the PLA plastic was printed as the mechanical structure, Ag/AgCl ink can be used as a conductive coating. Because of this special processing method, it holds substantial potential for personalized healthcare as shown in
Figure 7d [
93].
Figure 7. Typical common-contact electrodes. (
a–
d) Finger-shaped electrodes [
66,
91,
92,
93]; (
e,
f) brush-like electrodes [
94,
96]; (
g) 3D-printed electrodes [
97]; (
h–
j) textrodes [
100,
101,
102]; (
k) non-contacted electrodes [
88]; (
l,
m) multi-function electrodes [
107,
108].
To manage thick hair, there are also brush-like electrodes similar to finger-type electrodes. They have been widely studied for some time because of their good performance. Kitoko’s research [
94] provided a method using a reusable silver/silver chloride made with twelve 2 mm contact posts or bristles for EEG testing (
Figure 7e). The results did not reveal any significant differences between the two electrodes in all six subjects tested compared to wet electrodes. Grozea et al. [
95] proposed a bristle electrode by coating thin polymer bristles with silver particles. This kind of electrode can provide good contact with the scalp and good comfort. However, soft bristles are a double-edged sword. The conductive coatings can very easily to fall off due to the excellent flexibility of the bristles. Gao et al. [
96] designed a novel passive dry pin-shaped electrode consisting of a pedestal and bristles (
Figure 7f). The pedestal of the electrode was made of CNT-filled polydimethylsiloxane (PDMS-CNT), while the pins were fabricated from carbon fiber and PU with CNT doping. For the bristles, the carbon fiber would not easily break off due to the much higher modulus of elasticity than that of Ag or PDMS. Because of the small contact area of the pointed dry electrode, the subjects will feel uncomfortable. In addition, the coating is likely to fall off due to the flexibility of the probe or bristles. Other special structures that adapt to the shape of the hair and scalp can be made by 3D printing. Lee et al. [
97] printed a reverse-curve-arch-shaped dry EEG electrode consisting of 92.5% Ag and 7.5% Cu (
Figure 7g). The special shape can ensure the electrode overcomes the obstruction of hair effectively and the shortcomings of the limited contact area and pain induced of finger-shaped electrodes.
Besides the finger shape of pure metal, some methods are similar to conductive silica gel, in which conductive fillers are mixed into the matrix. Compared with the former, this method has a lower cost, and the comfort will be better due to the low modulus of the polymer substrate. There is no need for a complicated spring structure to adapt to the curvature of the scalp, but the flexibility of the material itself can adapt to the shape of the skull. Specifically, Krishnan et al. [
98] embedded carbon fiber into silicone foam owing to the biocompatibility and chemical inertness, which are appealing for use in EEG systems. Considering the conductivity, hardness, flexibility, and ease of fabrication, Chen et al. [
99] mixed an ethylene propylene diene monomer matrix with different additives such as carbon, stainless fibers, and carbon nanotubes. The skin electrodes’ impedance for 50% carbon content was about 10-fold higher than that of conventional wet electrodes, and the polymer electrodes containing 45% carbon had the best compromise between electrical and mechanical properties. The polymer electrodes showed nearly the same correlation and coherence as the wet electrode signals, but due to the high impedance, a lower SNR was obtained.
In addition, there are some new textile EEG electrodes, also named “textrodes”, that have gradually proved their feasibility in EEG acquisition due to their flexibility, stackability, and washability [
61]. The initial use of textile electrodes was for neonatal monitoring systems. For long-term EEG detection in newborns, the electrodes should not stimulate the sensitive skin of infants. However, any type of the former electrodes will inevitably bring about a pressure point. Therefore, textile electrodes came into being. These were originally used with a conductive paste, which suggests that they do not deviate from the category of “wet electrodes”. There are two electrodes proposed. The first one was knitted using a yarn containing 78% polyamide and 22% elastomer. The fabric was plated with 99% pure silver. The second one was made of 15% nylon, 30% silver-plated conductive fibers, 20% Spandex, and 35% polypropylene. The material was knitted and is similar to a terrycloth. However, the author did not consider the performance of the dry electrode after the conductive paste had dried [
100]. Similarly, Kumar et al. [
101] carried out the same research. Polyethylene terephthalate (PET) fabric was used as a substrate with a copper coating on it. The fabric layer encloses foam to ensure comfort for users. The SEM images show a very uniform deposition of copper on the fabric leading to good conductivity. However, electroless copper plating was carried out through multistep processes, including pre-treatment, sensitization, activation, electroless copper plating, post-treatment to stop copper reduction, rinsing, and drying. Lin et al. [
102] proposed a dry foam-based electrode for long-term EEG measurement by selecting urethane material as the matrix covered with 0.2 mm thick taffeta material made using electrically conductive polymer fabric. Finally, all surfaces were coated with Ni/Cu to establish electrical contact. The foam structure allowed high geometric conformity between the electrode and irregular scalp surfaces to maintain low skin–electrode interface impedance. Silver and copper are very popular among coating materials. In addition to pure metal particle coatings (
Figure 7h–j), there are also some ideas using graphene coating [
103] for ECG and polyaniline PANI [
104].
With the development of integration, there are still some dry electrodes only focusing on the hairless area, which are more lightweight. For example, Li coated Ag/AgCl onto a polyacetylimide substrate by screen printing [
105]. Jiang et al. [
106] used the electrically conductive composite of Ag flakes and PDMS on the silicon substrate. This method of conductive material attached to the thin flexible substrate is usually used in the hair-free area of the forehead, which can achieve the same performance as that of wet electrodes. With the development of the production process, some circuits including amplifiers and capacitors can be integrated into the substrate. At present, researchers can even combine other functions with EEG electrodes. For example, Lee et al. [
107] mixed silver nanowire and carbon nanotubes into PDMS (polydimethylsiloxane), forming an elastomeric conductive electrode that also acted as an earphone (
Figure 7l). Kappel et al. [
108] adopted a thermal iridium oxide film (TIROF) formed on an etched Ti surface as an electrode, and inserted it into holes in a soft earpiece as shown in
Figure 7m.
Flexible and composite materials are a current development trend in dry electrodes. These properties can maintain the electrodes’ high geometric conformity with the irregular scalp surface and are more portable. By this method, EEG acquisition and other functions can be integrated, which can also release the potential of BCI application as much as possible.