Photoelectric effect accelerated electrochemical corrosion and nanoimprint processes on gallium arsenide wafers.

Here we report photoelectric-effect-enhanced interfacial charge transfer reactions. The electrochemical corrosion rate of n-type gallium arsenide (n-GaAs) induced by the contact potential at platinum (Pt) and GaAs boundaries can be accelerated by the photoelectric effect of n-GaAs. When a GaAs wafer is illuminated with a xenon light source, the electrons in the valence band of GaAs will be excited to the conduction band and then move to the Pt boundaries due to the different work functions of the two materials. This results in an enhanced contact electric field as well as an enlarged Pt/GaAs contact potential. Consequently, in the presence of electrolyte solution, the polarizations of both the Pt/solution interface and the GaAs/solution interface at the Pt/GaAs/solution 3-phase boundary are enhanced. If the accumulated electrons on the Pt side are removed by electron acceptors in the solution, anodic corrosion of GaAs will be accelerated strictly along the Pt/GaAs/solution 3-phase boundary. This photo-enhanced electrochemical phenomenon can increase the corrosion rate of GaAs and accelerate the process of electrochemical nanoimprint lithography (ECNL) on GaAs. The method opens an innovative, highly efficient, low-cost nanoimprint technique performed directly on semiconductors, and it has prospective applications in the semiconductor industry.

Electrochemical nanoimprint lithography: when nanoimprint lithography meets metal assisted chemical etching.

The functional three dimensional micro-nanostructures (3D-MNS) play crucial roles in integrated and miniaturized systems because of the excellent physical, mechanical, electric and optical properties. Nanoimprint lithography (NIL) has been versatile in the fabrication of 3D-MNS by pressing thermoplastic and photocuring resists into the imprint mold. However, direct nanoimprint on the semiconductor wafer still remains a great challenge. On the other hand, considered as a competitive fabrication method for erect high-aspect 3D-MNS, metal assisted chemical etching (MacEtch) can remove the semiconductor by spontaneous corrosion reaction at the metal/semiconductor/electrolyte 3-phase interface. Moreover, it was difficult for MacEtch to fabricate multilevel or continuously curved 3D-MNS. The question of the consequences of NIL meeting the MacEtch is yet to be answered. By employing a platinum (Pt) metalized imprint mode, we demonstrated that using electrochemical nanoimprint lithography (ECNL) it was possible to fabricate not only erect 3D-MNS, but also complex 3D-MNS with multilevel stages with continuously curved surface profiles on a gallium arsenide (GaAs) wafer. A concave microlens array with an average diameter of 58.4 µm and height of 1.5 µm was obtained on a ∼1 cm2-area GaAs wafer. An 8-phase microlens array was fabricated with a minimum stage of 57 nm and machining accuracy of 2 nm, presenting an excellent optical diffraction property. Inheriting all the advantages of both NIL and MacEtch, ECNL has prospective applications in the micro/nano-fabrications of semiconductors.

Contact electrification induced interfacial reactions and direct electrochemical nanoimprint lithography in n-type gallium arsenate wafer.

Although metal assisted chemical etching (MacEtch) has emerged as a versatile micro-nanofabrication method for semiconductors, the chemical mechanism remains ambiguous in terms of both thermodynamics and kinetics. Here we demonstrate an innovative phenomenon, i.e., the contact electrification between platinum (Pt) and an n-type gallium arsenide (100) wafer (n-GaAs) can induce interfacial redox reactions. Because of their different work functions, when the Pt electrode comes into contact with n-GaAs, electrons will move from n-GaAs to Pt and form a contact electric field at the Pt/n-GaAs junction until their electron Fermi levels (EF) become equal. In the presence of an electrolyte, the potential of the Pt/electrolyte interface will shift due to the contact electricity and induce the spontaneous reduction of MnO4- anions on the Pt surface. Because the equilibrium of contact electrification is disturbed, electrons will transfer from n-GaAs to Pt through the tunneling effect. Thus, the accumulated positive holes at the n-GaAs/electrolyte interface make n-GaAs dissolve anodically along the Pt/n-GaAs/electrolyte 3-phase interface. Based on this principle, we developed a direct electrochemical nanoimprint lithography method applicable to crystalline semiconductors.

Electrochemical micro/nano-machining: principles and practices.

Micro/nano-machining (MNM) is becoming the cutting-edge of high-tech manufacturing because of the increasing industrial demand for supersmooth surfaces and functional three-dimensional micro/nano-structures (3D-MNS) in ultra-large scale integrated circuits, microelectromechanical systems, miniaturized total analysis systems, precision optics, and so on. Taking advantage of no tool wear, no surface stress, environmental friendliness, simple operation, and low cost, electrochemical micro/nano-machining (EC-MNM) has an irreplaceable role in MNM. This comprehensive review presents the state-of-art of EC-MNM techniques for direct writing, surface planarization and polishing, and 3D-MNS fabrications. The key point of EC-MNM is to confine electrochemical reactions at the micro/nano-meter scale. This review will bring together various solutions to "confined reaction" ranging from electrochemical principles through technical characteristics to relevant applications.

Confined Chemical Etching for Electrochemical Machining with Nanoscale Accuracy.

In the past several decades, electrochemical machining (ECM) has enjoyed the reputation of a powerful technique in the manufacturing industry. Conventional ECM methods can be classified as electrolytic machining and electroforming: the former is based on anodic dissolution and the latter is based on cathodic deposition of metallic materials. Strikingly, ECM possesses several advantages over mechanical machining, such as high removal rate, the capability of making complex three-dimensional structures, and the practicability for difficult-to-cut materials. Additionally, ECM avoids tool wear and thermal or mechanical stress on machining surfaces. Thus, ECM is widely used for various industrial applications in the fields of aerospace, automobiles, electronics, etc. Nowadays, miniaturization and integration of functional components are becoming significant in ultralarge scale integration (ULSI) circuits, microelectromechanical systems (MEMS), and miniaturized total analysis systems (µ-TAS). As predicted by Moore's law, the feature size of interconnectors in ULSI circuits are down to several nanometers. In this Account, we present our perseverant research in the last two decades on how to "confine" the ECM processes to occur at micrometer or even nanometer scale, that is, to ensure ECM with nanoscale accuracy. We have been developing the confined etchant layer technique (CELT) to fabricate three-dimensional micro- and nanostructures (3D-MNS) on different metals and semiconductor materials since 1992. In general, there are three procedures in CELT: (1) generating the etchant on the surface of the tool electrode by electrochemical or photoelectrochemical reactions; (2) confining the etchant in a depleted layer with a thickness of micro- or nanometer scale; (3) feeding the tool electrode to etch the workpiece. Scavengers, which can react with the etchant, are usually adopted to form a confined etchant layer. Through the subsequent homogeneous reaction between the scavenger and the photo- or electrogenerated etchant in the electrolyte solution, the diffusion distance of the etchant is confined to micro- or nanometer scale, which ensures the nanoscale accuracy of electrochemical machining. To focus on the "confinement" of chemical etching reactions, external physical-field modulations have recently been introduced into CELT by introducing various factors such as light field, force field, hydrodynamics, and so on. Meanwhile, kinetic investigations of the confined chemical etching (CCE) systems are established based on the finite element analysis and simulations. Based on the obtained kinetic parameters, the machining accuracy is tunable and well controlled. CELT is now applicable for 1D milling, 2D polishing, and 3D microfabrication with an accuracy at nanometer scale. CELT not only inherits all the advantages of electrochemical machining but also provides advantages over photolithography and nanoimprint for its applicability to different functional materials without involving any photocuring and thermoplastic resists. Although there are some technical problems, for example, mass transfer and balance, which need to be solved, CELT has shown its prospective competitiveness in electrochemical micromachining, especially in the semiconductor industry.

Electrochemical buckling microfabrication.

Can isotropic wet chemical etching be controlled with a spatial resolution at the nanometer scale, especially, for the repetitive microfabrication of hierarchical 3D µ-nanostructures on the continuously curved surface of functional materials? We present an innovative wet chemical etching method called "electrochemical buckling microfabrication": first, a constant contact force is applied to generate a hierarchical 3D µ-nanostructure on a mold electrode surface through a buckling effect; then, the etchant is electrogenerated on-site and confined close to the mold electrode surface; finally, the buckled hierarchical 3D µ-nanostructures are transferred onto the surface of a Ga x In1-x P coated GaAs wafer through WCE. The concave microlens, with a Fresnel structure, has an enhanced photoluminescence at 630 nm. Comparing with energy beam direct writing techniques and nanoimprint lithography, this method provides an electrochemical microfabrication pathway for the semiconductor industry, with low cost and high throughput.

A novel planarization method based on photoinduced confined chemical etching.

A photoinduced confined chemical etching system based on TiO2 nanotube arrays is developed for the planarization of the copper surface, which is proved to be a prospective stress-free chemical planarization method for metals and semiconductors.

A leveling method based on current feedback mode of scanning electrochemical microscopy.

Substrate leveling is an essential but neglected instrumental technique of scanning electrochemical microscopy (SECM). In this technical note, we provide an effective substrate leveling method based on the current feedback mode of SECM. By using an air-bearing rotary stage as the supporter of an electrolytic cell, the current feedback presents a periodic waveform signal, which can be used to characterize the levelness of the substrate. Tuning the adjusting screws of the tilt stage, substrate leveling can be completed in minutes by observing the decreased current amplitude. The obtained high-quality SECM feedback curves and images prove that this leveling technique is valuable in not only SECM studies but also electrochemical machining.

Electrochemical mechanical micromachining based on confined etchant layer technique.

The confined etchant layertechnique (CELT) has been proved an effective electrochemical microfabrication method since its first publication at Faraday Discussions in 1992. Recently, we have developed CELT as an electrochemical mechanical micromachining (ECMM) method by replacing the cutting tool used in conventional mechanical machining with an electrode, which can perform lathing, planing and polishing. Through the coupling between the electrochemically induced chemical etching processes and mechanical motion, ECMM can also obtain a regular surface in one step. Taking advantage of CELT, machining tolerance and surface roughness can reach micro- or nano-meter scale.

Electrochemically-driven large amplitude pH cycling for acid-base driven DNA denaturation and renaturation.

In this paper, we present an electrochemically driven large amplitude pH alteration method based on a serial electrolytic cell involving a hydrogen permeable bifacial working electrode such as Pd thin foil. The method allows solution pH to be changed periodically up to ±4~5 units without additional alteration of concentration and/or composition of the system. Application to the acid-base driven cyclic denaturation and renaturation of 290 bp DNA fragments is successfully demonstrated with in situ real-time UV spectroscopic characterization. Electrophoretic analysis confirms that the denaturation and renaturation processes are reversible without degradation of the DNA. The serial electrolytic cell based electrochemical pH alteration method presented in this work would promote investigations of a wide variety of potential-dependent processes and techniques.