This study presents a semiconducting optoelectronic system for light-controlled non-genetic neuronal stimulation using visible light. The system architecture is entirely wireless, comprising a thin film of nitrogen-doped ultrananocrystalline diamond directly grown on a semiconducting silicon substrate. When immersed in a physiological medium and subjected to pulsed illumination in the visible (595 nm) or near-infrared wavelength (808 nm) range, charge accumulation at the device-medium interface induces a transient ionic displacement current capable of electrically stimulating neurons with high temporal resolution. With a measured photoresponsivity of 7.5 mA W-1, the efficacy of this biointerface is demonstrated through optoelectronic stimulation of degenerate rat retinas using 595 nm irradiation, pulse durations of 50-500 ms, and irradiance levels of 1.1-4.3 mW mm-2, all below the safe ocular threshold. This work presents the pioneering utilization of a diamond-based optoelectronic platform, capable of generating sufficiently large photocurrents for neuronal stimulation in the retina.
Elevated temperature operation offers a promising avenue for enabling highly efficient water electrolysers. Combined with a high operating pressure to maintain water in the liquid phase, elevated temperatures can improve reaction kinetics and ionic transport and thus further reduce the electrical energy cost for green hydrogen. However, these working conditions can make it difficult to examine bubble dynamics and their impact on electrolyser performance. This paper describes the design and construction of a novel experimental research platform for investigating water electrolysis at up to 200 bar and up to 200 degrees C with optical access for imaging bubble dynamics. Important design challenges are described, including the incorporation of a viewing windows as well as the reliable control of cell compression. This new, optically accessible design enables us to investigate polarisation behaviour and bubble dynamics of over a wide range of working temperatures and pressures that extend well beyond current industrial practice.
Real time, chronic electrochemical detection of neurotransmitters will provide a positive step in the treatment and understanding of neurological disease. However, current electrodes using carbon fibers (CF) fail to perform chronically. While diamond-based coatings show promise in improving their longevity, achieving a uniform layer of such coatings on CFs is challenging, and the electrodes often lose sensitivity after coating. In this work, a complete and uniform boron-doped nanocrystalline material grown in a diamond reactor (B-NCD) was developed to coat CF microelectrodes for neurochemical sensing. The coating was characterized electrically, optically, mechanically, and chemically. The B-NCD coated CF electrodes were able to detect phasic dopamine at a sensitivity comparable to the most widely used alternatives (uncoated and PEDOT:Nafion coated CFs). During biofouling testing, the B-NCD coated CF electrodes demonstrated better stability than uncoated CFs and comparable performance to PEDOT:Nafion coated CFs. Moreover, B-NCD exhibited no signs of degradation during consecutive FSCV applications, while uncoated and PEDOT:Nafion coated CF electrodes degraded significantly over time. Furthermore, the B-NCD coating supported the survival and development of neurons and astrocytes in vitro, exhibited excellent adhesion and durability during mechanical bending testing, and enabled successful in vivo recording of phasic dopamine release in the rat brain. Overall, B-NCD coated CFs present as an ideal candidate for chronic, flexible neural implantable electrodes for long-term neurochemical monitoring.
The ability to form diamond electrodes on insulating polycrystalline diamond substrates using single‐step laser patterning and the use of these electrodes as a substrate that supports the adhesion and proliferation of human mesenchymal stem cells (hMSCs) are demonstrated. Laser‐induced graphitization results in a conductive amorphous carbon surface, rich in oxygen‐ and nitrogen‐terminated groups. This leads to an electrode with a high specific capacitance of 182 μF cm 2 , a wide water window of 3.25 V, and a low electrochemical impedance of 129 Ω cm 2 at 1 kHz—essential attributes for effective bioelectronic cell interfaces. The electrode's surface exhibits no cytotoxic responses with hMSCs, supporting cell adhesion and proliferation. Cells cultured on the electrode display significant elongation and alignment along the direction of the laser‐patterned microgrooves—an additional modality for cellular modulation. The combination of favorable electrochemical performance and effective cellular control makes laser‐patterned diamond electrodes a versatile platform in stem cell therapeutics. This direct fabrication approach paves the way for the integration of diamond electrodes in bioelectronic devices, offering new opportunities for tissue engineering and electroactive biomaterial applications.
In recent years, various forms of nanocrystalline diamond (NCD) have emerged as an attractive group of diamond/graphite mixed-phase materials for a range of applications from electron emission sources to electrodes for neural interfacing. To tailor their properties for different uses, NCD surfaces can be terminated with various chemical functionalities, in particular hydrogen and oxygen, which shift the band edge positions and electron affinity values. While the band edge positions of chemically terminated single crystal diamond are well understood, the same is not true for nanocrystalline diamond, which has uncontrolled crystallographic surfaces with a variety of chemical states as well as graphitic grain boundary regions. In this work, the relative band edge positions of as-grown, hydrogen terminated, and oxygen terminated nitrogen-doped ultrananocrystalline diamond (N-UNCD) are determined using ultraviolet photoelectron spectroscopy (UPS), while the band bending is investigated using photoelectrochemical measurements. In contrast to the widely reported negative electrode affinity of hydrogen terminated single crystal diamond, our work demonstrates that hydrogen terminated N-UNCD exhibits a positive electron affinity owing to the increased surface and bulk defect densities. These findings elucidate the marked differences in electrochemical properties of hydrogen and oxygen terminated N-UNCD, such as the dramatic changes in electrochemical capacitance.
This paper proposes a power system architecture and control for efficient and low-cost green hydrogen production. The proposed system integrates photovoltaic (PV) sources directly with an electrolyser stack, thereby eliminating the need for traditional power converters. With the removal of traditional power converters, maximum power point tracking is achieved through dynamic switching of electrolyser cells in the stack, enabling load variation to maintain optimal voltage for maximum power output. The demonstration methodology involves comprehensive MATLAB Simulink analysis of the integrated system performance through controlled PV-electrolyser interactions.
This study demonstrates the control of neuronal survival and development using nitrogen-doped ultrananocrystalline diamond (N-UNCD). We highlight the role of N-UNCD in regulating neuronal activity via near-infrared illumination, demonstrating the generation of stable photocurrents that enhance neuronal survival and neurite outgrowth and foster a more active, synchronized neuronal network. Whole transcriptome RNA sequencing reveals that diamond substrates improve cellular-substrate interaction by upregulating extracellular matrix and gap junction-related genes. Our findings underscore the potential of conductive diamond as a robust and biocompatible platform for noninvasive and effective neural tissue engineering.
Semiconducting electrodes are increasingly utilised for neural interfacing applications, such as neural recording, stimulation, and photomodulation. To characterize the performance of these electrodes, photoelectrochemical analysis is often undertaken in biologically relevant electrolytes. These include electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and for photomodulation applications, photocurrent (PC) measurements. From such measurements, it is possible to deduce key properties of semiconductor surfaces, such as electrochemical impedance and capacitance, as well as mechanisms of charge transfer. To extract these parameters from the experimental data, equivalent electrical circuit modelling is often employed, but usually only for a single technique at a time which often misses key insights about the processes occurring at the electrode-electrolyte interface. Here we present an equivalent circuit model that simultaneously describes the results from CV, EIS, and PC transient measurements. Using semiconducting nitrogen-doped ultrananocrystalline diamond (N-UNCD) electrodes in saline solution, we show that the model describes physical mechanisms that occur at the interface with electrolyte, encompassing the space charge region, the electrical double layer, and the electrolyte. Using the model we are able to optimize parameters relevant for neural interfacing and suggest that this framework may assist in the characterization of other semiconducting electrodes.
Electrical stimulation is one of several methods for controlling differentiation and proliferation of stem cells. This work demonstrated the use of nitrogen-doped ultra-nanocrystalline diamond (N-UNCD) electrodes as a substrate for the growth of human mesenchymal stem cells (hMSCs). As well as exhibiting a high charge injection capacity, N-UNCD displays high cytocompatibility making it suitable electrode material for stem cell stimulation.Clinical Relevance—This work establishes that N-UNCD electrodes can support the growth of hMSCs.
In the past 50 years, the advent of electronic technology to directly interface with neural tissue has transformed the fields of medicine and biology. Devices that restore or even replace impaired bodily functions, such as deep brain stimulators and cochlear implants, have ushered in a new treatment era for previously intractable conditions. Meanwhile, electrodes for recording and stimulating neural activity have allowed researchers to unravel the vast complexities of the human nervous system. Recent advances in semiconducting materials have allowed effective interfaces between electrodes and neuronal tissue through novel devices and structures. Often these are unattainable using conventional metallic electrodes. These have translated into advances in research and treatment. The development of semiconducting materials opens new avenues in neural interfacing. This review considers this emerging class of electrodes and how it can facilitate electrical, optical, and chemical sensing and modulation with high spatial and temporal precision. Semiconducting electrodes have advanced electrically based neural interfacing technologies owing to their unique electrochemical and photo-electrochemical attributes. Key operation modalities, namely sensing and stimulation in electrical, biochemical, and optical domains, are discussed, highlighting their contrast to metallic electrodes from the application and characterization perspective.
Durable and safe energy storage is required for the next generation of miniature bioelectronic devices, in which aqueous electrolytes are preferred due to the advantages in safety, low cost, and high conductivity. While rechargeable aqueous batteries are among the primary choices with relatively low power requirements, their lifetime is generally limited to a few thousand charging/discharging cycles as the electrode material can degrade due to electrochemical reactions. Electrical double layer capacitors (EDLCs) possess increased cycling stability and power density, although with as-yet lower energy density, due to quick electrical adsorption and desorption of ions without involving chemical reactions. However, in aqueous solution, chemical reactions which cause electrode degradation and produce hazardous species can occur when the voltage is increased beyond its operation window to improve the energy density. Diamond is a durable and biocompatible electrode material for supercapacitors, while at the same time provides a larger voltage window in biological environments. For applications requiring higher energy density, diamond-based pseudocapacitors (PCs) have also been developed, which combine EDLCs with fast electrochemical reactions. Here we inspect the properties of diamond-related materials and discuss their advantages and disadvantages when used as EDLC and PC materials. We argue that further optimization of the diamond surface chemistry and morphology, guided by computational modelling of the interface, can lead to supercapacitors with enhanced performance. We envisage that such diamond-based supercapacitors could be used in a wide range of applications and in particular those requiring high performance in biomedical applications.
Nitrogen-doped ultrananocrystalline diamond (N-UNCD) is a form of diamond electrode with near-infrared photoresponsivity, making it well suited for physiological applications. N-UNCD's photoresponsivity is strongly influenced by its surface. While it is known that oxygen treatment provides a higher photoresponsivity, a better understanding of its surface processes is needed to tailor the material for optical neuromodulation. This work examines the impact of various oxygen treatment methods, with aim of creating oxygen rich surfaces with different chemical and structural properties. Surface characterisation methods along with electrochemical and photoelectrochemical measurements and modelling were used to investigate the films. It was found that oxygen furnace annealing resulted in orders of magnitude improvement in the near-infrared photoresponsivity, to 3.75 ± 0.05 µA/W. This translates to an approximate 200 times increase in the photocurrent compared to the untreated surface. This enhancement in photocurrent is largely due to the changes in the chemical species present at the surface. The photocurrent is estimated to be sufficient for extra-cellular stimulation of brain neurons within the safe optical exposure limit, positioning N-UNCD as an excellent candidate to be used in next-generation photoelectrodes for photobiomodulation.
The electrochemical capacitance of nitrogen-doped ultrananocrystalline diamond (N-UNCD) can be dramatically increased by treating the surface with an RF-oxygen plasma. Such treated surfaces display excellent properties for use as electrodes in neural stimulation and recording. In the present work, we elucidate the origins of this phenomenon by investigating the effects of different methods of oxygen termination. We found that the increase in electrochemical capacitance is dependent on the details of the method used for oxygen termination. Whilst NUNCD subjected to UV/ozone treatment, oxygen plasma treatment, and furnace annealing in oxygen gas all displayed increased surface capacitance, the highest capacitance was exhibited by the oxygen annealed sample, with which we achieved similar to 3 orders of magnitude increase in the electrochemical capacitance as compared to the as-grown sample. The maximum recorded capacitance was 3746 +/- 132 mu F cm(-2), which is substantially greater than previously reported N-UNCD electrodes' electrochemical capacitance (1070 mu F cm(-2), W. Tong. et al, 2016). Our findings point to the presence of sub-surface solid state capacitance which contributes significantly to the observed electrochemical capacitance of the oxygen terminated N-UNCD electrodes. When combined with the favourable biocompatibility and inertness of the N-UNCD, our approach may provide a route towards the development of advanced neural sensing and stimulating electrodes.
Nitrogen-doped ultrananocrystalline diamond (N-UNCD) is a promising material for a variety of neural interfacing applications, due to its unique combination of high conductivity, bioinertness, and durability. One emerging application for N-UNCD is as a photoelectrode material for high-precision optical neural stimulation. This may be used for the treatment of neurological disorders and for implantable bionic devices such as cochlear ear implants and retinal prostheses. N-UNCD is a well-suited material for stimulation photoelectrodes, exhibiting a photocurrent response to light at visible wavelengths with a high charge injection density [A. Ahnood, A. N. Simonov, J. S. Laird, M. I. Maturana, K. Ganesan, A. Stacey, M. R. Ibbotson, L. Spiccia, and S. Prawer, Appl. Phys. Lett. 108, 104,103 (2016)]. In this study, the photoresponse of N-UNCD to near-infrared (NIR) irradiation is measured. NIR light has greater optical penetration through tissue than visible wavelengths, opening the possibility to stimulate previously inaccessible target cells. It is found that N-UNCD exhibits a photoresponsivity which diminishes rapidly with increasing wavelength and is attributed to transitions between mid-gap states associated with the graphitic phase present at the grain boundaries and the conduction band tail. Oxygen surface termination on the diamond films provides further enhancement of the injected charge per photon, compared to as-grown or hydrogen terminated surfaces. Based on the measured injected charge density, we estimate that the generated photocurrent of oxygen terminated N-UNCD is sufficient to achieve extracellular stimulation of brain tissue within the safe optical exposure limit.