Development of Memory Elements based on Surface-Modified

Nanostructured Porous Silicon

TOLAGAY DUISEBAYEV, MARGULAN IBRAIMOV, BAKYT KHANIYEV, AYAN TILEU,

DINA ALIMBETOVA

Department of Solid State Physics and Nonlinear Physics,

Al-Farabi Kazakh National University,

71 Al-Farabi Avenue, Almaty,

KAZAKHSTAN

Abstract: - Due to advancements in memory technology, nanostructured semiconductor-based memristors are

attracting increasing attention. This article presents the results of a study on memristors based on modified

porous structures made from silicon. The memristive properties of nanostructured porous silicon (por-Si) and

metal-oxide layers were investigated. The memristors based on por-Si were fabricated using electrochemical

etching. The study shows that after 3 minutes, the por-Si film exhibited reversible properties, indicating that

memristive behavior was observed in the porous silicon nanofilms. Metal-oxide semiconductor, such as CuO,

was deposited on the por-Si surface using magnetron sputtering. The morphology of the por-Si and

heterostructure was analyzed using scanning electron microscopy. The influence of light illumination on the

memristor properties of films was also observed, with an increase in the hysteresis area dependent on the

illumination process.

Key-Words: - memristor, porous silicon, nanofilm, electrical characteristics, hysteresis, magnetron sputtering,

memory elements, surface modification.

Received: April 4, 2024. Revised: August 5, 2024. Accepted: September 7, 2023. Published: Ovotber 17, 2024.

1 Introduction

Developing new semiconductor memory types is

essential in modern micro- and nanoelectronics

applications, [1]. Demand for low-power

electronic devices, such as memories, which

operate at lower voltages and exhibit ultra-high

speed with excellent flexibility, has increased

tremendously in this modern era. However, a

considerable gap exists between the amount of

created data and the available data storage space,

which must be satisfied. Hence, there is an

urgent requirement for a

promising alternative

that can effectively replace legacy technology

concerning device performance, flexibility, and

versatility. Memristor is considered one of the

best candidates for the next-generation high-

performance nonvolatile memory,

logic, and

neuromorphic applications, [2], [3], [4], [5].

Memristors are used in many electrical circuits [6],

[7], [8], neural networks [9], [10], [11] and

neurodynamics [12], [13] d ue to their simple

device structure, reliability, switching endurance,

fast reading, and writing. In addition, they are

widely applied in nanotechnology industries [14],

[15] for their nano-scale device dimensions, low

power consumption,

and excellent scalability. A

similar element was implemented in 2008 by

Stanley Williams (Hewlett-

Packard) group. It

was a thin (30–50 nm) bilayer TiO2/TiO2-x film

sandwiched between

platinum electrodes, [16].

The main characteristic of a memristor, as a

passive element of an electrical circuit, is that its

resistance is dependent on the integration of the

current flowing through it during operation. This

means that the element can “remember” the last

value of resistance when the power is switched

off. The estimated data retention time for this

memory is more than 10 years. Several

memristor models have been designed, which

include the resistive random-

access memories

[17], TiOx memristor [18], SiOx memristor [19],

[20], [21], [22], ZnO memristor [23], [24], NiO

[25], perovskites [26]. In addition to the

experimental studies, considerable attention has

been paid to the theoretical modeling of the

properties of memristors [27], [28], [29], [30].

Composite materials combining metal oxides along

with nanostructured porous materials, especially

porous silicon (por-Si), represent a suitable

platform for the fabrication of memrisitive

elements. Por-Si has a large specific surface area,

WSEAS TRANSACTIONS on ELECTRONICS

DOI: 10.37394/232017.2024.15.8

Tolagay Duisebayev, Margulan Ibraimov,

Bakyt Khaniyev, Ayan Tileu, Dina Alimbetova

E-ISSN: 2415-1513

Volume 15, 2024

fractal nature, and distinctive electrical properties

for creating memory cells. The advantage of using

por-Si is the simplicity of their production

technology and their compatibility with devices of

modern silicon microelectronics. In addition, it is

possible to control the characteristics of the por-Si

by changing the parameters of electrochemical

etching. Thus, by depositing metal oxides on the

por-Si surface and creating a heterojunction

structure, it is possible to improve its memristrive

performance at room temperature, [31]. In [32]

authors showed the memristive properties and

adjustable nature of memristors by embedding NiO

into a mesoporous silicon substrate and performing

a lateral current scan. Also, [33], reported a

memristive device fabrication from nanostructured

porous silicon-ZnO/VO2 composites. [34],

designed a bionic double-layer nanoporous

structure comprising a Pt/porous LiCoO2/porous

SiO2/Si stack which delivered high memristive

performance due to the unique electrochemical

properties of porous materials.

One of the most

attractive semiconductors that can improve the

memristive properties of por-Si is CuO due to its

electrical and optical properties. Although CuO

is one of the most essential semiconductors and

can be used in gas sensors, optical devices,

electronic materials, batteries etc., there are few

reports about its memristive properties. This

article discusses the creation of a new nanoscale

memristor based on surface-modified

nanostructured por-Si nanofilms.

2 Experimental Details

2.1 Porous Silicon Substrate Fabrication

Por-Si layers were obtained by electrochemical

etching using p-type boron-doped (100) silicon

wafers with a resistivity of 10 Ω∙cm and 2 × 10 mm2

dimensions. The electrochemical etching process

was laid out in a special electrochemical cell and

was monitored by the power supply. The

electrochemical cell is made of highly acidic

resistant polymer material such as Teflon. The

schematic diagram of the electrochemical etching

setup is depicted in Figure 1, [35].

The silicon wafers were dipped into HF (48 %)

acid for 5 sec and then cleared with ethanol to

remove the unwanted impurities from the surface.

The electrolyte solution consists of HF (48 %) acid

and ethanol in a volume ratio of 1:1, respectively.

The power supply unit has a voltage of 30 V and a

current of 5 mA. The etching time was 3 min.

Fig. 1: Electrochemical etching setup

The etched sample porosity was determined by

the gravimetric method using the formula (1):

   

 󰇛󰇜

where m1 is the weight of silicon before etching, m2

is the weight after electrochemical etching, and m3 is

the weight after the removal of porous layer in KOH

solution, [35].

2.2 Metal Oxide Layer Deposition

CuO layer was deposited on the surface of the por-

Si samples by magnetron sputtering technology.

Magnetron sputtering technology advantages are

fast deposition speed, deposited films well

combined with the substrates, and high purity. The

magnetron sputtering process was performed on the

Kurt J. Lesker LAB-18 magnetron system (Kurt J.

Lesker Company, Dresden, Germany). A CuO

target with a purity of 99.999% was used to mount

CuO on the por-Si surface, and the distance between

the target and the por-Si sample was 13 cm. The

base vacuum pressure of the unit was 5‧10-6 Torr,

and the working pressure was 10.5 mTorr. In

addition, argon (Ar) and oxygen (O2) gases were

introduced into the magnetron sputtering chamber

with flow rates of 40 sccm and 10 sccm,

respectively. The sputtering power of CuO was 100

W, and the deposition time was 30 min. After

depositing CuO on the surface of the por-Si sample,

the film was annealed in a special furnace at a

temperature of 650°C for 4 hours to obtain a

crystalline state.

2.3 Characterization

The morphology and composition of the adsorbents

were examined and analyzed by scanning electron

microscope (SEM) Quanta 200i 3D using SEM

images and EDX spectrum, respectively. Scanning

electron microscopy (SEM) images were used to

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DOI: 10.37394/232017.2024.15.8

Tolagay Duisebayev, Margulan Ibraimov,

Bakyt Khaniyev, Ayan Tileu, Dina Alimbetova

E-ISSN: 2415-1513

Volume 15, 2024

determine the shape and thickness of the fabricated

samples.

The NI ELVIS II+ module was used to measure

the current-voltage characteristics of the samples in

the voltage range U = 0 – 3 V; the measurement step

was 10 mV. The hysteresis behavior in the current-

voltage characteristics of the samples was obtained

by Keysight B1500A Semiconductor Analyzer. Two

ohmic contacts of InGa alloy in the coplanar

configuration were deposited on the samples’

surface by thermal installation to obtain electrical

characteristics as shown in Figure 2.

Fig. 2: Configuration of contacts for measurements

3 Results and Discussion

Figure 3 shows cross-sectional and top-view SEM

images of the por-Si sample, which was etched for 3

min. Due to electrochemical etching in hydrofluoric

acid, the pores were formed with a thickness of 5.16

μm. It can be seen from Figure 2b that pores and air

voids are randomly distributed over the entire

surface. The porosity value of the por-Si sample was

calculated by formula (1) and amounted to 52.6%.

Fig. 3: Cross-sectional (A) and top-view (B) SEM

images of the

por-Si

sample

We performed EDX measurements in

conjunction with SEM to analyze the chemical

composition of nanostructured material. The result

of this study is presented in Figure 4. Silicon is the

powder's dominant element.

Fig. 4: EDX spectrum of por-Si sample

SEM images of por-Si and CuO/por-Si samples

are shown in Figure 5. As can be seen from the

figure, the CuO layer which was installed on the

surface of the por-Si sample also has a porous

structure. Consequently, the pores of the por-Si

substrate are not completely closed, which provides

a higher surface area and a diffusion channel.

Fig. 5: Cross-sectional (A) and top-view (B) SEM

images of the CuO/por-Si samples

Figure 6 shows the current-voltage

characteristics of the por-Si sample with

measurement intervals of 15 s, 18 s, 1 min, and 3

min, respectively, and shows a positive shift in the

current-voltage characteristics after each

measurement. It shows that the electrical properties

of the por-Si sample depend on the applied voltage

and the previous state. After 3 min, the current value

of the film returns to its initial state (reset).

Accordingly, it is found that the typical memristive

behavior of the por-Si sample can be analyzed based

on the measurement results. Figure 7 shows the

current-time dependence at a voltage of 1.2 V.

At this stage, the phenomenon of hysteresis

allows using memristors as memory cells. In some

aspects of electronics, they will probably be able to

replace semiconductor transistors. The theoretical

model described in this work is more

straightforward than the modeled theory in

published work, [28].

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Tolagay Duisebayev, Margulan Ibraimov,

Bakyt Khaniyev, Ayan Tileu, Dina Alimbetova

E-ISSN: 2415-1513

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Fig. 6: Current-voltage characteristics at different

time intervals, where (1) Initial state, (2) 15 sec, (3)

18 sec, (4) 1 min, (5) 3 min

Fig. 7: Current-time dependence at 1.2V

Obtaining nanostructured por-Si films with the

properties of a memristor is more accessible than

getting structures based on TiO2 and ZnO. The por-

Si memristor does not have the problems of three-

terminal memristors [19], such as relatively low

switching speed, high power consumption, and lack

of a high-density massive structure. In a previous

paper [36], the authors of this paper pointed out the

presence of hysteresis curves of current-voltage and

capacity-voltage characteristics of semiconductor

films based on por-Si. The data obtained indicate

the memristive properties of the films. So far, we

obtained similar physical properties for

semiconductor films based on por-Si with the

addition of CuO.

The resulting por-Si film also had a hysteresis in

the current-voltage characteristics, as in [36]. It was

also found that the hysteresis area increased when

this film was illuminated by a xenon lamp Oriel

Sol3A (I = 0.1 W/cm2, λVS). Hysteresis in the

current-voltage characteristics of the por-Si are

shown in Figure 8.

Fig. 8: The current-voltage characteristics of por-Si

in the dark (1) and under illumination (2)

CuO/por-Si sample was also exposed to light

from a xenon lamp. Exposure to radiation increases

the hysteresis area several times, indicating the

film’s large memristive properties. Graphs and

calculations of the hysteresis area in the current-

voltage curves are shown in Figure 9:

Fig. 9: The current-voltage characteristics of

CuO/por-Si in the dark (1) and under illumination

(2)

The hysteresis areas were processed and

calculated using the Origin package, and their

analytical form is presented as follows, [37]:



󰇻 

 󰇻  󰇻 

 󰇻   󰇻 

 󰇻(2)

As mentioned earlier, the hysteresis curves

indicate the presence of memristance properties, and

the larger the area, the better these properties

manifest. The comparison tables of hysteresis areas

depending on illumination are shown in Table 1.

According to data presented in Table 1, the

illumination of the films contributes to an increase

in the memristor properties. The hysteresis area

increases almost 10 times after illumination for the

por-Si sample and 2 times for CuO/por-Si.

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Tolagay Duisebayev, Margulan Ibraimov,

Bakyt Khaniyev, Ayan Tileu, Dina Alimbetova

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Table 1 Hysteresis areas dependency on

illumination

Hysteresis

areas

Samples

Por-Si

CuO/

por-Si

1.06

5.09

11.2

10.7

S2/S1

10.6

2.1

The properties of films based on por-Si suggest

they could be used to create memory cells with

optical control. The observed increase in hysteresis

when exposed to light is attributed to numerous

defects and traps on the por-Si surface, which are

crucial for current transfer within the por-Si

structure. The nonlinear hysteresis seen in the

current-voltage characteristics of these materials is a

result of potential barriers within their structure.

Additionally, the hysteresis area expands due to the

photocurrent generated by incident photons. Photons

have enough energy to lift an electron from the

valence band to the conduction band. Thus, when

light falls on the surface of the samples, their

conductivity increases, which leads to an increase in

hysteresis. The hysteresis observed in the current-

voltage characteristics suggests that resistive

switching is mainly driven by the electrochemical

migration of oxygen ions through a conduction path

within the porous materials, [33]. The deposition

and annealing process of CuO leads to the

generation of oxygen vacancies. As diffusion

constants depend on particle size, with diffusion in

bulk being much slower than in nanoparticles due to

shortened transport paths, confinement of the metal

oxides to a nanoscale size enhances the ionic

transport within the porous channels, [38].

4 Conclusion

To conclude, por-Si holds great potential for

advancing silicon-based memristive structures,

offering a wide array of future applications. The

results showed that with appropriate modification,

for example by introducing a metal oxide on the

surface, improved memristive properties can be

achieved. In this work the typical memristive

behavior of nanostructured por-Si and metal oxide

layer deposited on it was demonstrated and

analyzed. Additionally, it was found that obtaining a

por-Si nanofilm with memristive properties is

simple and does not require additional efforts to

develop the device. It was also observed that the

hysteresis areas in the current-voltage characteristics

of CuO/por-Si significantly increased when exposed

to illumination. These characteristics facilitate the

development of memory cells and crossbar

structures with optical control. Thus, modified

nanostructured semiconductors based on por-Si can

be essential in successfully implementing practical

memristors using economical materials and simple

fabrication technologies.

Acknowledgement:

This research is funded by the Ministry of Science

and Higher Education of the Republic of

Kazakhstan, grant number: AP19678266.

Declaration of Generative AI and AI-assisted

Technologies in the Writing Process

During the preparation of this work the authors used

Grammarly and DeepL platforms in order to check

the grammar of sentences and improve the language

of the manuscript. After using this tool/service, the

authors reviewed and edited the content as needed

and take full responsibility for the content of the

publication.

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Contribution of Individual Authors to the

Creation of a Scientific Article (Ghostwriting

Policy)

The authors equally contributed to the present

research, at all stages from the formulation of the

problem to the final findings and solution.

Sources of Funding for Research Presented in a

Scientific Article or Scientific Article Itself

This research is funded by the Ministry of Science

and Higher Education of the Republic of

Kazakhstan, grant number: AP19678266.

Conflict of Interest

The authors have no conflicts of interest to declare.

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(Attribution 4.0 International, CC BY 4.0)

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WSEAS TRANSACTIONS on ELECTRONICS

DOI: 10.37394/232017.2024.15.8

Tolagay Duisebayev, Margulan Ibraimov,

Bakyt Khaniyev, Ayan Tileu, Dina Alimbetova

E-ISSN: 2415-1513

Volume 15, 2024