1 s2.0 S0042207X23007650 Main
1 s2.0 S0042207X23007650 Main
Vacuum
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A R T I C L E I N F O A B S T R A C T
Handling Editor: Prof. L.G. Hultman To alleviate the von Neumann architecture bottleneck, scholars have proposed neuromorphic computing con
sisting of artificial synapses and neural network algorithms, in which the ability to well simulate biological
Keywords: synaptic functions is considered a key step in building neuromorphic computing. In this work, the artificial
SrTiO3 synapse based on Al-doped SrTiO3 (STAO) thin film is fabricated by a low-cost sol-gel method. It effectively
Memristor
emulated a diverse array of significant synaptic functions, including spike-time-dependent plasticity and short/
Artificial synapse
long plasticity. We constructed a convolutional neural network (CNN) to perform the training/recognition task of
Neuromorphic computing
handwritten digit images and demonstrated the applicability of the memristor device in neuromorphic
computing. We compared STAO with SrTiO3 (STO) and found that the Al-doped devices had better stability,
higher linearity, and higher image recognition accuracy from 84.5% to 96.2%. We have studied the main
influencing factors for these improving performances, which may be due to the generation of more oxygen
vacancies by Al doping. The x-ray photoelectron spectroscopy (XPS) test showed an increase in the oxygen
vacancy content of the sample from 23.59% to 37.91%, which supports our hypothesis. This has positive ram
ifications for building artificial neural networks capable of processing vast quantities of data.
* Corresponding author.
E-mail address: [email protected] (W.-H. Li).
https://doi.org/10.1016/j.vacuum.2023.112568
Received 29 May 2023; Received in revised form 28 August 2023; Accepted 30 August 2023
Available online 31 August 2023
0042-207X/© 2023 Elsevier Ltd. All rights reserved.
Z.-H. Shen et al. Vacuum 217 (2023) 112568
samples by Al doping and investigated their synaptic-related properties microstructure. Using X-ray Photoelectron Spectroscopy (XPS) (Escalab
such as long/short term plasticity. We constructed Au/STAO/LNO/Si 250Xi, Thermo Fisher, England) analyze the element’s chemical state
artificial synapses and realized the simulation of various synaptic [28,29]. The binding energy was calibrated by the work function
memory learning functions. In addition, to evaluate the possibility of method [30,31]. The spectra were shifted accordingly so that the C 1s
artificial synaptic devices in artificial neural networks, a convolutional peaks were aligned at (289.58 − ΦSA) eV, where ΦSA was obtained from
neural network (CNN) was constructed and used to recognize hand the literature for the work function of the sample with a value of 4.5 eV
written digit images, achieving an accuracy rate of 96.2%, demon [32]. The source gun type was monochromatic Al Kα. The electron
strating its feasibility for neuromorphic computation [2,22,23]. emission angle is 58◦ , and the sample analysis area size is 650 μm. The
instrument base pressure is 3 × 10− 7 mBar, and a charge neutralizer is
2. Experimental section used. Characterization of the sample cross-section morphology by
transmission electron microscopy (TEM) (Talos F200X G2, FEI, Amer
The experiments were performed by the sol-gel method, which ica). Additionally, the electrical performances of the samples were
mainly involved the processes of precursor solution preparation, film evaluated using Keithley 2400 (Solon, OH, America) [33].
shaking by a homogenizer, baking by heating platform, and annealing
by annealing equipment [24–26]. 3. Results and discussion
2.1. Precursor solution preparation 3.1. Structure, morphology, and chemical states
LaNiO3 precursor solution: Nickel acetate Ni(OCOCH3)2⋅4H2O and Fig. 1 shows the surface morphology of the STAO and STO thin film.
lanthanum nitrate La(NO3)3⋅6H2O were adopted as raw materials, It can be seen from Fig. 1(a) that the STAO thin film is dense, smooth and
ethylene glycol methyl ether C3H8O2 and glacial acetic acid C2H4O2 as uniform with very high crystallinity and the grain size is about 70 nm.
solvents, and acetylacetone C5H8O2 as a stabilizer. Dissolve the desired The cross-sectional morphology (See Fig. S1 for details) of the thin film
raw materials in a 1:1 solvent. Stir for 1 h until the solute was completely is illustrated in Fig. 1(e), the interface of STAO/LNO heterostructure is
dissolved. clearly layered, the thickness of STAO is about 230 nm, and the thick
SrTi0.9Al0.1O3-δ precursor solution: Tetrabutyl titanate ness of LNO is about 130 nm. By comparing Fig. 1(a) and (b), the grain
C16H36O4Ti, strontium acetate C2H3O2Sr, aluminum acetylacetonate size of the Al-doped STAO thin film is larger and more dense. The
C15H21AlO6 were adopted as raw materials, ethylene glycol methyl ether elemental composition of the facets of STAO was determined by energy
C3H8O2 and ice acetic acid C2H4O2 as solvents, and acetylacetonate dispersive spectroscopy (EDS), as shown in Fig. 1(c). It was found that
C5H8O2 as a stabilizer. Firstly, C2H3O2Sr was dissolved in C3H8O2 and the elements were uniformly distributed in the sample, which indirectly
C2H4O2 and stirred for 2 h at 60 ◦ C, C15H21AlO6 was dissolved in C2H4O2 indicated that the thin film samples were well grown. More details can
and stirred for 1 h at 50 ◦ C, C16H36O4Ti was dissolved in C5H8O2 and be found in Fig. S2. In addition, Fig. 1(d) shows the AFM image of the
stirred for 15 min at room temperature. Finally, the three solutions were STAO sample surface, which exhibits a smooth and uniform morphology
mixed together and stirred at room temperature for 35 min. with a root-mean-square roughness (Rq) of 3.98 nm. The AFM plot of the
SrTiO3 precursor solution: The preparation process is the same as STO sample is presented in Fig. 1(f), and its Rq is 2.73 nm. The result of
for SrTi0.9Al0.1O3-δ precursor solution but without the addition of Al. comparison shows that Al doping results in larger grains and higher Rq
All three precursor solutions mentioned above were at a concentra of the sample [34,35], which corresponds to SEM (Fig. 1(a) and (b)).
tion of 0.25 mol/L and left at room temperature for three days to ensure Fig. 1(g) depicts the 3D schematic of the Au/STAO/LNO/Si device.
no precipitation before being used to prepare the films [27]. To investigate the impact of Al doping on the chemical valence and
ratio of the sample elements, narrow spectra were scanned for Sr 3d, Ti
2.2. Thin film preparation 2p, O 1s and Al 2p of the samples. Fig. 2(a) illustrates the detection of
two discernible peaks of Sr 3d at 133.18 eV and 134.98 eV, signifying
Substrate cleaning: Experiments were performed using p-Si sub the presence of the Sr2+ state [36]. The Al spectrum is shown in Fig. 2
strates, which were cleaned with acetone, anhydrous ethanol, and iso (d), with a peak at 73.88 eV, indicating the Al3+ state [37]. As indicated
propanol in an ultrasonic bath for 35 min at room temperature. Each in Fig. 2(b) and (c), the sample has two main peaks near 463 eV and 458
cleaning in the ultrasonic bath was followed by several repeated rinses eV for Ti 2p3/2 and Ti 2p1/2, respectively, suggesting the dominance of
with deionized water to ensure a clean substrate. This is because the Ti4+ ions. In the STAO sample, additional shoulder-like features appear
cleanliness of the substrate is an important factor in the quality of the which are attributed to the Ti3+ state [38,39]. The decrease in Ti valence
thin film. state indicates the existence of oxygen vacancies. A brief defect reaction
Preparation of thin films: The substrate was placed on a Spin equation can be written to deepen the understanding of the Al ion
Coater, and an appropriate amount of precursor solution was added doping effect [40,41]:
dropwise onto the substrate by aspirating it with a syringe; the Spin
1
Coater speed was set to 1000 rpm for 15 s and 4000 rpm for 40 s. The wet VO2− ⟶VO.. + 2e′ + O2 (1)
2
film was placed on a baking platform at 100 ◦ C for 10 min and at 400 ◦ C
for 20 min in order to make the precursor solution in organic matter 2Ti4+ + 2e′⟶2Ti3+ (2)
decompose sufficiently to ensure the formation of nuclei within the film.
Repeat the above steps several times, depending on the required film Al3+ ′ 1
thickness. Finally, the films were annealed at 800 ◦ C for 20 min. SrTiO3 → Al SrTiO3 + VO.. + O2 (3)
2
2.3. Characterization and measurement where VO2− represents lattice oxygen and VO.. represents oxygen
vacancies.
The X-ray Diffraction (XRD) (D8 ADVANCE, Bruker, Germany) was The lowering of the Ti valence state indicates that the Al element in
used to analyze the crystal structures of the samples with an incidence the sample successfully replaced the Ti element and caused oxygen va
angle of 0.5◦ , a scan step of 0.02◦ , a scan time of 30 min, and a scan angle cancies at the same time [39,41,42]. It is also evidenced by the obser
range of 20◦ –80◦ . Scanning Electron Microscopy (SEM) (SUB8220, vation of O 1s spectra. Fig. 2(e) and (f) depict the O 1s spectrum
Hitachi, Japan) and Atomic Force Microscope (AFM) (Dimension featuring a low binding energy (LBE) peak and a high binding energy
FastScan, Bruker, America) were performed to characterize the sample
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Z.-H. Shen et al. Vacuum 217 (2023) 112568
Fig. 1. (a) and (b) SEM pictures of the sample microstructure. (c) The STAO sample’s EDS spectrum results. (d) and (f) show the two-dimensional and three-
dimensional AFM images. (e) Cross-section of the STAO sample. (g) Schematic illustration of the Au/STAO/LNO/Si device.
Fig. 2. XPS spectra of the STAO thin films: (a) Sr 3d, (b) Ti 2p, (d) Al 2p, (e) O 1s. XPS spectra of the STO thin films: (c) Ti 2p, (f) O 1s.
(HBE) peak [43]. The former is attributed to lattice oxygen, whereas the (111), (200), (220), (222), and (311) were seen in the XRD pattern
latter may be caused by oxygen vacancies in the thin films [41,43]. A (Fig. 3), in agreement with the data reported (JCPDF Card No. 35-0734),
comparison of the O 1s spectra of STO and STAO thin films revealed that showing the standard cubic phase. It is noteworthy that no significant
Al doping induced a boost in the amount of oxygen vacancies (from shift in the peak position of STAO was observed, which is likely due to
23.59% to 37.91%), which could enhance the synaptic performance of the low content of doped elements.
the devices [44].
The phase structure of the sample was analyzed by XRD test. Peaks
3
Z.-H. Shen et al. Vacuum 217 (2023) 112568
The synaptic structure in the human brain neural network and the
artificial synaptic device structure are depicted in Fig. 4. The device is
not only structurally similar to the biological synapse but also func
tionally similar. Both are three-layer structures, and the device
conductance corresponds to the synaptic weight; biologically, the syn
aptic weight is varied by internal Na + Ca2+ migration [45], while the
conductance of the device depends on the migration of oxygen vacancies
[46,47].
The electrical properties of the device are evaluated through the Fig. 5. (a) The process of formation and breakage of conductive filaments. (b)
application of a voltage or a designed pulsed sequence to the top elec Single I-V measurement curve of device. (c) I–V curve plotted on a double
trode. As shown in Fig. 5(b), the device is capable of showing successive logarithmic scale.
and regular changes under voltage sweeps, which means that the
conductance state of the device can be dynamically tuned. This feature Fig. 5(a). By treating the samples with a focused ion beam, possible
holds significant application potential for simulating biological regions of CF were found as depicted in Fig. S3.
synapses. The device’s double-logarithm fitting analysis, as shown in Fig. 5(c),
Changes in synaptic weight in biology are caused by changes in in was performed for studying more about the carrier transport mecha
ternal ion concentrations, while changes in the conductivity of the de nism. When the voltage is scanned from 0 V to 6 V, the device is at a high
vice are caused by oxygen vacancies [36,48–50]. Vacancies migrate and resistance state (HRS) and the slope is 1.12, which is linear, indicating
progressively form conductive filaments (CF) [51,52] under the influ that the ohmic transport mechanism is followed at this time, and as the
ence of voltage. Changes in voltage lead to the formation and breaking of voltage increases, the slope rises to 4.63, which follows space charge
filaments [53–55], resulting in changes in conductivity, as shown in limited conduction (SCLC) [56,57]. Subsequently, the device is at a low
resistance state (LRS) as the voltage is scanned positively from 6 V to 0
V, with a slope close to 1, suggesting that the ohmic conduction mech
anism is followed. In addition, the 100 I-V cycle test of the device is
illustrated in Fig. S4, and the STAO device has better stability and
durability.
4
Z.-H. Shen et al. Vacuum 217 (2023) 112568
Fig. 6. The I-V curves of positive and negative voltage sweeps are displayed in (a) and (b). Current modulation under (c) positive and (d) negative consecutive
triangular wave.
5
Z.-H. Shen et al. Vacuum 217 (2023) 112568
Fig. 8. (a) Schematic illustration of the input and output signals of PPF. (b) Variation of PPF index with time interval. (c) The input pulse schematic of STDP. (d)
Synaptic weights fitted with time.
following formula: Where A0 and A1 are the conductance values before and after applying a
I2 − I1 pulse to the device, respectively. Δw represents the change in synaptic
PPF = × 100% (4)
I1 weight. The fitted curve of STDP is represented by the dotted line in
Fig. 8(d) and can be described by the following equations:
The PPF data obtained from the experiment and the corresponding
{
fitted PPF index curve are presented in Fig. 8(b). The equation used for C1 exp(− t/τ1 ), Δt > 0
fitting the PPF to the pulse interval is presented in equation [60]: STDP = (7)
C2 exp(− t/τ2 ), Δt < 0
PPF = A1 ∗ exp(− t/τ1 ) + A2 ∗ exp(− t/τ2 ) (5)
The results suggest that the Δw of the device decreases with
The t is time interval. τ1 and τ2 are 82 ms and 786 ms, respectively, increasing Δt, meaning the shorter the stimulus interval, the more sen
which closely match the relaxation time of human brain synapses [61]. sitive the synaptic response. This is in accordance with the Hebbian
As shown in Fig. 8(b), the PPF growth rate increases from 101% to 127% synaptic learning rule, and the device exhibits STDP.
as the time interval decreases. This demonstrates the enhanced
short-term synaptic weight modulation when the signal interval of 3.4. Application: Identifying handwritten digits
synaptic transmission is short enough, a behavior that is very similar to
the role of neurotransmitter release in synapses. To test the aptitude of artificial synaptic devices for employment in
In brain neural activity, electrical stimulation can not only neuromorphic computing, a convolutional neural network (CNN) was
strengthen or weaken synapses, but also generate a range of functions constructed and used to recognize images in the MNIST dataset [64,65].
associated with space and time. One of the typical properties when As shown in Fig. 9(a), our CNN has three convolutional layers for feature
implementing synaptic learning functions is their ability to conform to map extraction, three pooling layers for redundant information reduc
one of the important synaptic adaptation rules in Hebbian theory, Spike- tion, and one fully connected layer for image classification [66]. The
timing-dependent plasticity (STDP), and also necessary to implement network consists of 784 inputs neurons, 256 hidden neurons and 10
when simulating brain functions in neuromorphic computation [62,63]. outputs neurons for distinguishing numbers between 0 and 9 [67–69].
Hence, accurate simulation of the STDP learning rule is an important The handwritten digital images in the MNIST dataset are shown in Fig. 9
requirement for the development of brain-like synaptic devices. The (b), which includes 60,000 images, 48,000 for training, and 12,000 for
design of the pre/post-synaptic membrane pulses is in Fig. 8(c). testing. We mapped the measured device conductance to the numerical
Fig. 8(d) depicts the simulated results of STDP, where a pair of pre/ weights of the neural network and obtained the recognition rate after
post-synaptic spikes with amplitudes of +/- 4 V, respectively, were 100 epochs. Fig. 9(c) shows the variation of the image recognition ac
applied to the device. The change in synaptic weight (Δw) was measured curacy of the simulated network with training time. We compared the
as a function of the relative time (Δt) between the two spikes. The recognition rates of STAO and STO, and it is clear that the recognition
definition of Δw, given by accuracy obtained based on the synaptic data of Al-doped samples is
higher, indicating that Al doping facilitates the artificial synaptic de
A1 − A0
Δw = × 100% (6) vices to exhibit better performance, which is very meaningful.
A0
6
Z.-H. Shen et al. Vacuum 217 (2023) 112568
Fig. 9. (a) Convolutional neural network framework diagram. (b) Handwritten digital image of the MNIST dataset. (c) Recognition accuracy based on STAO and
STO samples.
In conclusion, the Au/STAO/LNO/Si memristor prepared by the sol- Supplementary data to this article can be found online at https://doi.
gel method is capable of achieving functions of biological synapses like org/10.1016/j.vacuum.2023.112568.
STP, LTP, PPF, and STDP. We constructed a CNN to train the MNIST digit
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