Meng
Qi‡
a,
Runze
Xu‡
a,
Guanglong
Ding
b,
Kui
Zhou
b,
Shirui
Zhu
a,
Yanbing
Leng
a,
Tao
Sun
a,
Ye
Zhou
b and
Su-Ting
Han
*c
aInstitute for Microscale Optoelectronics, Shenzhen University, Shenzhen 518060, P. R. China
bInstitute for Advanced Study, Shenzhen University, Shenzhen 518060, P. R. China
cDepartment of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong, China. E-mail: suting.han@polyu.edu.hk
First published on 29th November 2023
Being capable of processing large amounts of redundant data and decreasing power consumption, in-sensor computing approaches play significant roles in neuromorphic computing and are attracting increasing interest in perceptual information processing. Herein, we proposed a high performance humidity-sensitive memristor based on a Ti/graphene oxide (GO)/HfOx/Pt structure and verified its potential for application in remote health management and contactless human–machine interfaces. Since GO possesses abundant hydrophilic groups (carbonyl, epoxide, and hydroxyl), the memristor shows a high humidity sensitivity, fast response, and wide response range. By utilizing the proton-modulated redox reaction, humidity exposure to the memristor induces a dynamic change in the switching between high and low resistance states, ensuring essential synaptic learning functions, such as paired-pulse facilitation, spike number-dependent plasticity, and spike amplitude-dependent plasticity. More importantly, based on the humidity-induced salient features originating from the abundant hydrophilic functional groups in GO, we have implemented a noncontact human–machine interface utilizing the respiratory mode in humans, demonstrating the potential of promoting health monitoring applications and effectively blocking virus transmission. In addition, the high recognition accuracy of contactless handwriting in a 5 × 5 array artificial neural network was successfully achieved, which is attributed to the excellent emulated synaptic behaviors. This study provides a feasible method to develop an excellent humidity-sensitive memristor for constructing efficient in-sensor computing for application in health management and contactless human–computer interaction.
New conceptsA new-type of humidity-sensitive memristor is constructed based on the structure of Ti/GO/HfOx/Pt, which has potential for use in health management and contactless human machine interfaces. Using moisture-electric annealing, GO not only acted as a center for the accumulation of water molecules, but also induced the formation of internal electrical field. This induced electrical field both accelerated the movement of O2− and increased the conductance of the memristor, which made it possible to modulate the migration of O2− to mimic the plastic behaviors, such as paired-pulse facilitation, spike number-dependent plasticity, and spike amplitude-dependent plasticity, making it inherently more biological. This device can be further controlled by utilizing respiratory stimulation, indicating its potential for application in health management. In addition, the humidity-sensitive memristor successfully demonstrated excellent contactless handwriting in an artificial neural network. The proposed approach has potential to provide novel platforms for the development of artificial sensory neurons, which is of great significance for non-contact human–computer interaction in intelligence applications. |
Inspired by the biological perception system with a data-centric tactic, in-sensor computing architectures bring an innovative concept to improve the evaluation efficiency of humidity-indicated health management because the sensory data can be locally filtered, memorized, and processed without shuttling.14,17–19 Stimuli in the form of humidity bind to receptor cells to generate action potentials, which induce the release of neurotransmitters from the receptor cells to afferent neurons for further processing.20–22 For in-sensor computing, an intelligent device should be capable of simultaneously sensing, filtering, memorizing, and processing the humidity signal at the device level.22–26 In addition, the dynamic response in various humidity environments with a high sensitivity, fast speed, and long-term memory is highly demanded. Two-terminal memristors are especially suitable for in-sensor computing because of their several advantageous features of inherent dynamics, including a high speed switching,27,28 low energy consumption,29,30 high-density integration,31 and scalability.32,33 The conductivity of memristor encoded sensory information serves as synaptic weights.34,35 By collecting the cumulative output conductance of the memristor in a cross array, matrix vector multiplication can be accomplished in a single clock cycle taking advantage of the Ohm's law and Kirchhoff's law.36–39 Hence, high parallelism can be easily obtained with reduced latency and power consumption. However, traditional memristors based on a metal oxide switching layer exhibit low sensitivity to humidity since water is inadequate for driving the migration of anions in the resistive switching layer.1,40,41 Integrating the materials with highly hydrophilic nature and pronounced conductance changes upon humidity variation as the switching layer of memristors is expected to achieve controllable physicochemical behavior under adsorption/desorption of water molecules.
In this work, a high-performance humidity-sensitive memristor was proposed with the structure of Ti/graphene oxide (GO)/HfOx/Pt and was simultaneously verified to have the capability for application in remote health management and contactless human–machine interface. Since GO possesses abundant hydrophilic groups (carbonyl (CO), epoxide (C–O–C), and hydroxyl (C–OH)),1,42,43 the memristor shows high humidity sensitivity (795.31%, C90% relative humidity (RH)/C40%RH × 100%), fast response (0.1 s), and a wide response range (20% to 95%) (for details, see Note 1 in the ESI†).1,44 In addition, the humidity exposure of the memristor evokes the dynamic change in switching between the high conduction state (HRS) and low conduction state enabled via proton-modulated redox reaction, ensuring the possibility of synaptic functions imitated such as paired-pulse facilitation (PPF), spike number-dependent plasticity (SNDP), and spike amplitude-dependent plasticity (SADP). Based on the multifunctionality and reconfigurability of the memristor, we further design an integrated array to demonstrate its applications in respiratory monitoring systems and contactless gesture recognition systems.
Fig. 2a illustrates the schematic of the proposed memristor with the structure of Ti/GO/HfOx/Pt. The Ti as the adhesion layer and Pt as the BE were orderly deposited on the SiO2 substrate by magnetron sputtering. A 15 nm HfOx film was then manufactured by ALD. GO nanosheets were prepared according to the Hummers’ method presented in the previous report.49 Subsequently, the well dispersed GO solution was spin-coated the surface of the HfOx film to form a densely packed GO film. Finally, 50 nm Ti TEs with a diameter of 300 μm were deposited on the switching layer. Details of the fabrication process of the memristor are described in the Methods section. The AFM images show that the single GO sheet exhibits a flat surface and small roughness of Ra = 6.97 nm (Fig. 2b). Fig. 2c depicts the cross-sectional transmission electron microscope (TEM) image and energy-dispersive spectroscopy (EDS) of GO-HfOx, where the continuous surface of each layer was verified. As a comparison, the corresponding EDS mapping of O in the region before and after the action of the electric field is recorded. Obviously, the appearance of oxygen gradient originates from the electrical treatment of the GO layer. There is no different contrast in the top region of GO, which may be responsible for adsorbing and retaining water.42,43
Fig. 2d depicts the working mechanism of the GO-HfOx memristor, which can be well controlled via the proton sources by changing the RH. By application of a positive bias on the Ti TE, oxygen ions (O2−) dissociate from HfOx and migrate from the Pt BE towards the Ti TE under an external electric field, giving rise to the growth of oxygen vacancy (Vo) conductive filaments (CFs) in the HfOx-GO layer with the gradual increase of oxygen content from the TE to the BE.50–52 Under exposure to humidity, the GO film adsorbs water molecules owing to its oxygen-containing groups with strong hydrophilicity (e.g., –OH and –COOH) and this strategy is defined as moisture-electric annealing.43 The accumulation of water molecules in the O-rich region of GO films induces the regional solvation effect, which further breaks the O–H bond to release free protons (H+).42,43 The free H+ further migrate from the TE towards the BE along the oxygen gradient in the GO film and induce the formation of internal electrical field. This induced electrical field tends to accelerate the migration of O2− and establishment of Vo CFs, which further increases the conductance of the memristor. Thus, our HfOx-GO memristor can emulate the humidity-modulated plastic behavior of sensory synapse with increased RH.
The atomic ratio (C/O) of the as-deposited GO film after moisture-electric annealing was investigated by XPS (see Fig. S1 in the ESI† for more details). As summarized in Fig. 2e, the C/O atomic ratio gradually increases along the direction of the electric field, indicating the reduction of GO. Further, humidity-controlled electrical behaviors were investigated by complex impedance spectroscopy (CIS). Fig. 2f shows the CIS of the GO humidity sensor under different RH levels from 40% to 90%. At a lower RH of 40%, the larger curvature radius of the curve in the CIS plot stemming from the intrinsic impedance of the sensing film can be observed. According to Anderson's proton conductivity model, the hydrophilic group (i.e., C–O–C) of GO can only absorb a small amount of water molecules in this case; thus, the surface is not completely covered by water to release fewer H+.42,53 With increasing humidity RH from 60% to 90%, a portion of a semicircle gradually appears in the CIS curve, and moreover, the higher RH (60%–90%) results in a more obvious linear behavior on the curved tail wing, indicating that the intrinsic impedance decreases with increased RH, which may be attributed to the release of H+.53,54 As a result, the phenomenon of dependence of conductivity on humidity has great potential for a humidity-sensitive memristor for the applications of health monitoring and contactless human–machine interaction.
To understand the synaptic properties of our memristor under humidity stimuli, the Ti/GO/HfOx/Pt memristor was employed to emulate the basic synaptic functions including PPF, SNDP, SADP, and spike duration-dependent plasticity (SDDP) of biological humidity synapse. Fig. 3a schematically illustrates the biological synapse that connects pre- and postsynaptic neurons where the connection strength of the synapse can respond dynamically under moisture stimulus (i.e., synaptic plasticity), standing for the neurochemical basis of learning and memory. The TE/BE of the memristor can be functionally considered as presynaptic/postsynaptic neurons, the RS layer serves as a synaptic gap and the continuously controlled conductivity of the memristor is analogous to synaptic plasticity. The continuous modulation of conductance states was first demonstrated by applying the train of 10 voltage pulses with an amplitude of 1.5 V, duration of 5 ms and interval of 5 ms on the device under a fixed ambient RH of 40%, as shown in Fig. 3b and c. The current of the GO/HfOx memristor increases/decreases gradually under positive/negative sweeps, which is a synaptic memristor. Then, with the fixed positive/negative voltage scan from 0 V to 6 V to 0 V (Fig. 3d), the ambient moisture could be used as a stimulus to modulate the set voltage (VSET) of the memristor from ∼5.2 V to ∼1.2 V with RH increasing from 20% to 95%. In addition, the resistance of the HRS decreases with the increased RH value. The statistical data of stability and reliability is shown in the ESI† (Fig. S2). When the negative sweep voltage was applied from 0 V to −2 V to 0 V (Fig. 3e), the negative differential resistance effect of decreasing current with increasing voltage was observed since the switching channel changes from fast Vo CFs to slow proton conductive CFs.
It is well established that the synaptic plasticity in biology could be affected by the frequency, intensity, and duration of stimuli;55,56 thus, the modulation of pulse interval time, amplitude and duration time is deliberate on the humidity-sensitive memristor for modulating the conductance. As shown in Fig. 3f, greater variations in conductivity could be attained with the increase of humidity (RH ∼ 50% → RH ∼ 90%; 1 V, 5 ms), which is consistent with the biological synaptic behavior (for more details, see Fig. S3, ESI†).26,57,58 Furthermore, the PPF function with correlations between the temporal spike pair was further investigated in response to the humidity stimulus (for detailed PPF information, see Fig. S4, ESI†).59,60 As presented in Fig. 3g, excitatory postsynaptic current (EPSC) as the foundation of synaptic weight on the variation was evoked by monitoring the response to two moisture pulses with RH values of 50% and 95%, duration of 0.5 s and interval of 0.5 s. The second moisture pulse (RH ∼ 95%) arrives before the complete disappearance of the first EPSC, which accelerates the diffusion and accumulation of H+ within GO, leading to higher conductance changes. Thus, the peaks of EPSC excited by the second moisture pulse (A2) were obviously larger than that of the first pulse (A1). The higher EPSC in Fig. 3h reflects the remarkable synaptic enhancements through a larger humidity pulse width (0.5 s, 1 s, and 2 s), while it takes longer to recover the final state after removing the humidity pulse (RH range from 90% to 50%) representing the long-term memory effect of the human brain. In order to emulate long-term potentiation characteristics under modulation of RH, a pulse train of 50 electrical pulses with an amplitude of 1 V/−1 V and duration of 5 ms were applied as the presynaptic spikes (Fig. 3i). The nonlinearity is calculated to be 1.70768 (50%RH), 1.54824 (60% RH), 1.03238 (70% RH), 1.0209 (80% RH), 2.78658 (90% RH), which is the key parameter for a synapse to the realization of weight updating approach to high-level in-sensor computing (see ESI,† Note 2, for discussion of nonlinearity).61–63 The above results indicate that the reported humidity-sensitive memristor may be in accord with the characteristics of artificial synapses and provide a feasible strategy for the development of neuromorphic sensors for artificial intelligence.
We further expanded the application in respiratory monitoring systems by utilizing humidity sensitive memristors since many respiratory diseases including bronchitis, pneumonia, respiratory disturbance syndrome (SAS), and chronic obstructive pulmonary disease (COPD) are life-threatening. Fig. 4a shows the schematic diagram of an integrated respiratory monitoring system based on our memristor which can sense, memorize and process respiratory data (i.e., normal, COPD, and SAS) simultaneously. First, the current of the memristor was recorded with application of moisture-encoded ventilation mode including rapid, normal, and deep breathing of healthy people from exercise, normal, and relaxation states, as shown in Fig. 4b. From the slow-breathing rate of ∼12 per minutes to a fast-breathing rate of up to ∼120 breaths per minute (blue line), the memristor exhibits highly distinguished current responses with different delay times, frequencies and amplitudes. Moreover, the current response is strongly distinguishable between healthy people and patients with respiratory diseases. For example, the patients with COPD exhale drier gas than normal healthy people within one breath since the airway and throat of COPD patients is permanently blocked. In addition, the inspiratory and expiratory time of patients with COPD will be significantly lower than that of healthy humans, while the inspiratory flow will be remarkably restricted because of bronchospasm, etc. Therefore, detecting and processing various respiratory parameters of samples via our memristor can effectively differentiate between COPD patients and healthy people. In the breathing scheme, moisture pulses with a RH of 90%/RH of 80% and duration of 50 ms are utilized to mimic the breath of healthy people/COPD patients for implementing respiratory stimuli on the device, as illustrated in Fig. 4c. The output current responses caused by external stimuli in identical directions are distinguishing. Current spikes with a high rate (2 Hz) and amplitude variation (0.2281 μA) to achieve saturation state is biologically analogous to the case of COPD patients because their respiratory rate is relatively faster. Compared to the feedback from COPD patients, the current spikes of healthy people are at lower rate (0.5 Hz) with amplitude variation (0.1671 μA). Furthermore, the potential application of the humidity-sensitive memristor based respiratory monitoring system for monitoring SAS function is demonstrated in Fig. 4d. The typical current response of SAS patients was recorded by application of 1 V voltage, where the blue and red markers represent the signals of normal breathing and apnea, respectively. As shown, the apnea process correlates with a smaller current level compared with normal breathing, which is a great impetus to the diagnosis of apnea syndrome.
Besides the respiratory monitoring, we designed a 1 × 3 crossbar array of the humidity-sensitive memristor for the application of a gesture recognition system to address the motion of fingers by combining time coding effect. Different humidity fields of skin with a RH range from ∼98% to ∼45% can be induced by distance modulation from 2 mm to 10 mm between fingers and devices (Fig. 5a, schematic of finger movement in the insets of Fig. 5a). Fig. 5b presents the post-synaptic currents (PSCs) as a function of finger movement time. With the finger approaching the memristor, the moving signal can be detected as a presynaptic spike to generate current output with an amplitude of approximately 14.68 μA and saturation time (ST) of 1.13 s, respectively. To further investigate the distance correlation of the PSC/ST, the peak current/response time (RT) was collected and compared, as shown in Fig. 5c. It is worthwhile mentioning that the humidity synaptic device with memory effect is capable of generating current that is inversely proportional to the distance changes. The PSC/ST variation range from 14.68 μA to 2.48 μA/1.13 s to 3.54 s can be modulated by approaching distance from 2 mm to 10 mm, providing the basis for recognition of gestures.
Furthermore, we utilized a 1 × 3 memristor array to sense and process humidity information by decoding the distance between the finger and the device as well as the direction of finger movement, as shown in Fig. 5d. The noncontacting finger motions including drawing left, drawing right, enlargement, and shrinking can be recognized by the gesture recognition system. By collecting the humidity information from the memristor at different grid points, the feature vector was constructed depending on the onset time, which can be expressed as T = [ta, tb, tc]. The detected signal current vector can be expressed as P = [PSCa, PSCb, PSCc]. When the longitudinal spacing is fixed, the amplitude of output current correlates with the RH, which varies with increased distance between the finger and device. The vector concatenate of T and P provides the six-dimensional vectors F = [wa, wb, wc, PSCa, PSCb, PSCc] (w = tspiking/tmovement × 100%) as the input vector. F vector is first collected from the memristor array and then fed into a software-simulated fully connected artificial neural network (ANN) with six inputs and four outputs for final recognition, in which the input neurons are connected with 12 hidden neurons. The conjugate gradient backpropagation of Fletcher–Reeves was utilized as the weight update algorithm (see ESI,† Note 3, for discussion of the algorithm).64Fig. 5e shows a flowchart of the perception learning using the ANN computing process. The learning steps are described as follows: (1) input data is fed into the input layer (F, as the input data); (2) the activation function of sigmoid is utilized to transfer data from the hidden layer to the output layer; (3) the median error between the network output data and the actual data is calculated; (4) the loss and gradient is calculated by using the gradient descent algorithm for minimizing losses; (5) the ΔW is updated (the updated value of the hidden layer weight). The learning process stops when the accuracy is greater than 99% or the accuracy is not improved after 5 times continuous iteration. The system returns to step 2 to implement the next iteration if the end condition was not reached. The confusion graph for the 1st and 45th recognition is, respectively, shown in Fig. 5f and g. The confusion matrix for 4 labels of the target class and output class is validated. After the 1st training, the label “left” is only 10% correctly recognized (Fig. 5f), while the correct recognition rate of that after the 45th training is 100% (Fig. 5g). In contrast to the conventional calculation methods, higher recognition accuracy (98.75%) after 45 training epochs is displayed in Fig. 5h.
Next, we have implemented a feature extraction and learning architecture that provides a new strategy for sensing and processing technology. A typical ANN utilizing a fully connected method was established for performing the handwriting recognition with a finger close to the device in a 1 cm device spacing, as shown in Fig. 6a and b. An ANN schematic image consisting of the humidity-memristive synapse 5 × 5 arrays with three neuron layers (25 input neurons × 40 hidden neurons × 26 output neurons) is shown in Fig. 6a. The input information is transmitted to a neural network classifier via the PSC and pre-synaptic current (PrSC). Conductance variations are used as the input layer of the ANN (defined as W = (PSC − PrSC)/PSC × 100%). The W of each memristor can reflect the input trajectory of handwritten letters, which is related to the distance of fingers from the device (Fig. 6b). It is worth mentioning that the entire system has a near-sensor computing architecture, which can be used for real-time humidity collection and detection of finger-proximity patterns. The training process for handwritten letter recognition is performed based on conjugate gradient backpropagation with Fletcher–Reeves updates and the recognition accuracy is displayed in Fig. 6c.64,65 During the backpropagation process, the weights were updated in the repeated epochs of training until the error was decreased. Notably, the recognition accuracy of handwritten letters rapidly increased from 64.231% to 94.423% induced by the increase of iterations from 10 to 40 cycles and reached the saturation state. Fig. 6d shows the weights of each device in the 5 × 5 array for the recognition of the letter ‘A’ in the in-senor computing. This is further supported by the noise of dataset for the training shown in the ESI† (Fig. S5). In this realization, the confusion graph building block for the construction of ‘A’ ‘B’ ‘C’ ‘D’ ‘E’ five letters from the alphabet of 26 different strokes or different curvatures of the same stroke is displayed in Fig. 6e. The recognition accuracy can still reach more than 94% (see Fig. S6 and S7 in the ESI† for more details). This result suggests that our sensing memristors have the capability for handwritten recognition with a high accuracy in ANNs.
Footnotes |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3mh01734f |
‡ M. Qi and R. Z. Xu contributed equally to this work. |
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