Accepted Manuscript

Biodegradable skin-inspired nonvolatile resistive switching memory based on gold

nanoparticles embedded alkali lignin

Wei Wu, Suting Han, Shishir Venkatesh, Qijun Sun, Haiyan Peng, Ye Zhou, Chichung
Yeung, Robert K.Y. Li, V.A.L. Roy

PII: S1566-1199(18)30273-8
DOI: 10.1016/j.orgel.2018.05.051
Reference: ORGELE 4711

To appear in: Organic Electronics

Received Date: 26 January 2018

Revised Date: 27 April 2018
Accepted Date: 28 May 2018

Please cite this article as: W. Wu, S. Han, S. Venkatesh, Q. Sun, H. Peng, Y. Zhou, C. Yeung, R.K.Y.
Li, V.A.L. Roy, Biodegradable skin-inspired nonvolatile resistive switching memory based on gold
nanoparticles embedded alkali lignin, Organic Electronics (2018), doi: 10.1016/j.orgel.2018.05.051.

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1 Biodegradable skin-inspired nonvolatile resistive switching

2 memory based on gold nanoparticles embedded alkali lignin

4 Wei Wu,a Suting Han,b Shishir Venkatesh,a Qijun Sun,a Haiyan Peng,c Ye Zhou,d

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5 Chichung Yeung,e Robert K. Y. Li a,∗ and V. A. L. Roy a, ∗

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6
a
7 Department of Materials Science and Engineering, and State Key Laboratory for Millimeter

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8 Waves, City University of Hong Kong, Hong Kong SAR.
b
9 College of Electronic Science and Technology, Shenzhen University, Shenzhen 518060, China.

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10 Key Laboratory for Material Chemistry of Energy Conversion and Storage, School of Chemistry
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11 and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074,

12 China.
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13 Institute for Advanced Study, Shenzhen University, Shenzhen 518060, China

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14 Department of Chemistry, City University of Hong Kong, Hong Kong SAR.
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∗
Corresponding author.
E-mail addresses: aprkyl@cityu.edu.hk (Robert K. Y. Li), val.roy@cityu.edu.hk (V. A. L. Roy)
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1 ABSTRACT:

2 Natural biomaterials are capable of producing biodegradable and/or biocompatible electronic

3 devices for vast applications such as next-generation green data storage. Here, we demonstrate an

4 environment-friendly alkali lignin as a favourable candidate for resistive switching memory

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5 storage applications. The resistive memory devices based on gold nanoparticles embedded alkali

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6 lignin (Au NPs:lignin) exhibits a typical write-once-read-many-times memory (WORM) resistive

7 switching behaviour with a large on-off ratio (> 5 X 103), and long data retention characteristics (>

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8 103 s) under low power operation (4.7 V). Au NPs acting as trapping sites in the active layer are

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9 responsible for the resistive switching mechanism. The active layer is fabricated on organic
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10 substrates through facile solution-processed methods under normal ambient conditions. The

11 skin-inspired polylactide (PLA) film is utilized as an ultrathin substrate endowing the memory
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12 devices with good mechanical support and biodegradability. This work opens up new avenues
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13 towards renewable and environmentally benign lignin-based materials for biodegradable

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14 electronic devices.

15
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16 Keywords: alkali lignin, gold nanoparticles, polylactide, write-once read-many-times,

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17 biodegradable
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1 1. Introduction

2 Organic resistive switching memory has been regarded as a promising candidate for the

3 next-generation information storage because of the outstanding features including simple device

4 fabrication process, sustainability, fast switching capability and flexibility [1-4]. Compared to

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5 other memories, the resistance states of nonvolatile resistive switching memory can be read

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6 non-destructively without the need of power supply to maintain the programmed state [5, 6].

7 Although these attractive characteristics have been successfully demonstrated in organic small

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8 molecules, polymers, and polymer/inorganic hybrid materials, it is highly desirable to develop

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9 green information storage devices using natural biomaterials so as to minimize the negative
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10 environmental footprint from electronic waste. Several types of natural biomaterials, such as

11 cellulose [7], chitosan [8, 9], silk [10], protein [11-13], enzyme [14, 15] and DNA[16] have been
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12 employed as active layers in resistive switching memory devices. Such sustainable, biodegradable,
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13 biocompatible and eco-friendly materials can be fabricated through simple techniques for memory
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14 devices. Nevertheless, the application of such biomaterials often requires the use of toxic organic

15 solvents and/or harsh processing environment conditions.

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16 Lignin, which is the second most abundant biopolymer available from plants, consists of
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17 three phenylpropanoid units [17]. It is well known as a usually-discarded byproduct from the pulp
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18 and paper industry [18]. Alkali lignin (Fig. S1), as a major derivative of lignin, can be derived

19 from liquor waste of the modern Kraft pulping process. Recently, applications of economical

20 alkali lignin have been extended to electrolyte, energy storage, memory and chemical sensors

21 [19-23]. Park and Lee prepared resistive switching random access memory (ReRAM) and

22 artificial synaptic devices with pristine lignin [19, 24]. However, these devices showed a low

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1 ON/OFF ratio, which indicated that the data was easy to be misread. Recently many metallic

2 nanoparticles have been embedded into ogranic memory structures, such as gold, silver, copper,

3 aluminum [25-27]. These metal nanoparticles based organic memory devices have advantages of

4 higher density of states around the Fermi level and a wide range of available work, which means

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5 larger ON/OFF ratio and long retention time can be achieved [28-30]. Herein, gold nanoparticles

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6 embedded in the biodegradable alkali lignin (Au NPs:lignin) matrix are employed to realize

7 resistance switching devices. The following four reasons suggest that our choice is feasible. (1)

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8 Alkali lignin is an insulator in the native state [31]. Appropriate amount of Au NPs in polymer

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9 matrix can act as charge-trap elements to control the conductivity of the film [32]. (2) Abundance
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10 of carbonyl, hydroxyl and methoxy groups on the carbon side chains of alkali lignin qualifies the

11 alkali lignin to be dissolved in water which then allows for easy device processing [33]. (3) The
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12 existance of thiol groups in alkali lignin can cap the Au NPs to form covalent bonds, which will
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13 contribute to the charge tunneling acrcoss the Au NPs in the active layer and the contracts between
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14 the Au NPs and the electrodes [34-36]. (4) Alkali lignin can be easily processed as uniform and

15 stable films under normal conditions in air [37].

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16 To endow good mechanical properties to the designed resistive switching memory,

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17 polylactide (PLA) is employed as the substrate. PLA is a thermoplastic aliphatic polyester, which
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18 is 100% derived from renewable resource [38]. Due to its excellent biodegradability,

19 biocompatibility and non-toxicity, PLA has been utilized in various biomedical applications,

20 including drug delivery systems, bone fixation, surgical sutures and implants [37]. Currently, there

21 is a growing interest in using PLA as a promising eco-friendly alternative to prepare

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1 environmentally-friendly, sustainable and disposable electronics. For instance, there are reports of

2 PLA has applied as the substrate for inverters and dielectric layer in transistors [39, 40].

3 In the present work, the Al/Au NPs: lignin/Al sandwiched structure was used to investigate

4 the resistive switching effect. PLA is employed as a skin-inspired substrate, which endows the

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5 nonvolatile resistive switching memory devices with good mechanical support and

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6 biodegradability. Such skin-inspired memory based on alkali lignin shows great potential for

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7 radio-frequency identification tag (RF-ID), artificial electronic skin, and biomedical device

8 applications.

9 2. Experimental
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10 2.1. Materials and device preparation
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11 The alkali lignin, sodium citrate, gold chloride hydrate, 1,4-dioxane,

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12 trichloro(1H,1H,2H,2H-perfluorooctyl)silane and proteinase K were purchased from

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13 Sigma-Aldrich and used without further purification. The PLA (Ingeo 4032D) was supplied by

14 Natureworks (USA). SiO2 wafers were immersed in silane solution (15 µL of

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15 trichloro(1H,1H,2H,2H-perfluorooctyl)silane in 15 mL chloroform) to form a release monolayer.

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16 The remained silane was washed by rinsing in chloroform, acetone, 2-propanol, respectively. Then
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17 PLA with 10 wt% in 1,4-dioxane was coated on the SiO2 wafer via spin-coating at 1000 rpm for

18 60 s. The synthesis of Au NPs about 12 nm was prepared following the reported seed-mediated

19 growth method (Fig. S2 in Supporting Information) [41]. The finally obtained Au NPs

20 concentration was of 5 mM/L in deionized water. The alkali lignin powder was ultrasonically

21 dissolved in the Au NPs water solution with a fixed concentration of 50 mg/ml and then filtered

22 through 0.22 µm PTFE filter. The Au NPs:lignin solution was deposited on the PLA substrate with
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1 the bottom Al electrode by spin coating method at 3000 rpm for 60 s to prepare a resistive

2 switching layer. The remaining Au NPs in Au NPs:lignin matrix is about 0.61 wt% (Fig. S3 in the

3 Supporting Information). The average thickness of the deposit Au NPs:lignin layer was about 320

4 nm measured at three different areas using a spectroscopic ellipsometry. Finally, the top Al

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5 electrode was deposited on the top of the active layer to form a metal-insulator-metal (MIM)

structure with an active area of 1 × 1 mm2. For the 100 nm Al electrodes, the thermally deposit

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7 rate was controlled at a constant of 2 Å•s-1. The dimension of the shadow mask channel was 1 mm

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8 × 70 mm.

9 2.2.Characterization and measurement

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10 The properties of alkali lignin were tested by FTIR (Nicolet Nexus 670), TGA (Netzsch TG
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11 209F3) and XPS (Physical Electronics PHI 5802 spectrometer) (Fig. S4 in Supporting

12 Information). The electrical characteristics of the memory devices were measured by a

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13 semiconductor parameter analyzer (Agilent 4155C) under ambient temperature. The thickness of
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14 PLA layer was tested by a step profilometer (AMBIOS XP-2). The size distribution of Au NPs
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15 was verified by TEM (JEOL JEM-2100F). AFM with tapping mode (VEECO Multimode V) was

16 used to assess the surface morphology of the films. The HOMO and LUMO of Au NPs:lignin
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17 layer was characterized by a UV-Vis-NIR spectrophotometer (Agilent 8454) and an X-ray

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18 photoelectron spectrometer with UPS model (Kratos, Axis Ultra DLD). The surface potential

19 energy was evaluated by Kelvin probe force microscopy (KPFM, Bruker Dimension ICON) with

20 a SCM-PIT tip. The enzyme degradation test was conducted in DI water with 80 µg/ml proteinase

21 K. The temperature of the solution was kept at 55 °C.

22 3. Results and discussion

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1 The device fabrication of Au NPs:lignin resistive switching memory is schematically

2 illustrated in Fig. 1a. The simple metal-insulator-metal (MIM) cell structure is employed to

3 demonstrate the resistive switching effect. Fig. 1b shows the surface morphology of Au NPs:lignin

4 layer. A smooth surface with a small root mean square (RMS) surface roughness of 0.6 nm

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5 indicates well-dispersed Au NPs in the lignin layer. To ensure the device performance, an ultrathin

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6 film of PLA with a thickness of approximately 7 µm and RMS surface roughness of less than 0.3

7 nm (Fig. S5 in Supporting Information) was used as a skin-like flexible substrate. The fabricated

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8 flexible memory device is easy to peel off from the rigid substrate because of the

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9 trichloro(1H,1H,2H,2H-perfluorooctyl)silane self-assembled hydrophobic monolayer coated on
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10 the surface of SiO2 sacrificial substrate (Fig. 1c) [42]. The fabricated skin-inspired memory

11 device can be pasted on the arm directly indicating its good flexibility (Fig. 1d).
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12 The alkali lignin-based nonvolatile memory exhibits typical resistance switching

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13 characteristics under a direct voltage sweeping mode as shown in the current-voltage (I-V) curve
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14 (Fig. 2a). The applied voltage was carried out as 0 → +5 → 0 → −5 → 0 V with compliance
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15 current of 1 mA. Initially, the device keeps at a state of low current and the current increase

16 slightly during the first voltage swept from 0 to 4.7 V (stage I). When the voltage reaches the
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17 threshold value of 4.7 V (stage II), the current increases sharply from 1.56 × 10−8 to 1.90 × 10−4
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18 A, during which the device switches to low resistance state (LRS) from the high resistance state

19 (HRS). The transition of resistance state can be regarded as a writing process for the memory

20 device. The subsequent voltage scanning from stage III to stage IV shows the good stability of the

21 memory device in the LRS, indicating the data cannot be erased after writing process. These

22 results suggest that the device based on alkali lignin behaves as a write-once read-many-times

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1 (WORM) nonvolatile memory, which is quite different with the pure lignin memory (Fig. S6 in

2 Supporting Information). Of particular note that the ON/OFF current ratio of the alkali

3 lignin-based memory is as large as ~5 × 103, suggesting the unlikelihood of misreading of the data.

4 The data retention capability of the memory devices is evaluated by a continuous reading bias of

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5 0.6 V at room temperature in order to examine the device reliability. There is no obvious

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6 deterioration in retention property in HRS and LRS currents during the test (Fig. 2b), indicating

7 the robustness of the memory. The performance of this Au NPs/lignin memory was also compared

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8 with previous biodegradable materials based memory devices (Table. S1 in Supporting

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9 Information).
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11 Fig. 1. (a) Schematic flow chart of the fabricated alkali lignin-based memory device. (b) AFM

12 image of Au NPs embedded alkali lignin layer with RMS of 0.6 nm, indicating the smooth surface.

13 (c) Digital image of peeling off device from the SiO2 substrate. (d) Digital image of the memory

14 pasted on the arm.

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1 To elucidate the carrier transport mechanism of the WORM memory device, the

2 experimental I-V curves and fitting results are given in Figure 3a. In the low voltage region

3 (region A), the plots of In (I) vs. V1/2 from 0 to 2.75 V show the linear relationship with a slope of

4 0.65 (Fig. 3b), implying that the electron transport process may be followed by the thermionic

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5 emission conduction mechanism,[43]

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−(φ − q qV 4d πε )
I ∝ AT 2 exp[ ]
6 kT (1)

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7 where I is the current, A is the effective Richardson constant, T is the temperature, φ is Schottky

8 barrier height, q is the electron charge, V is the applied voltage, d is the film thickness, ε is the

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9 dielectric constant of the film, and k is Boltzmann constant. This result indicates that the charge

10 injection from the Al electrode to Au NPs:lignin active layer is dominant [44]. The highest
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11 occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of Au
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12 NPs:lignin determined by the ultraviolet photoelectron spectroscopy (UPS) and UV-Vis-NIR

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13 spectra are -6.85 and –4.22 eV, respectively (Fig. S7 in Supporting Information). The

14 corresponding indirect band gap (Eg) of Au NPs:lignin is 2.63 eV, which is calculated via
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15 Kubelka-Munk function [45]. On the other hand, only a small amount of carriers can overcome
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16 the energy barrier between the work function of Al electrode and the lowest unoccupied molecular
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17 orbital (LUMO) level of the Au NPs:lignin in the low voltage region [46]. With a further increase

18 in the bias voltage from 2.75 to 4.60 V (region B), a straight line with a slope of 1.33 can be well

19 fitted for the plots of log (I) vs log (V) (Fig. 3c). It is considered that the conduction mechanism

20 for the device may change to the trap-controlled space charge-limited current (SCLC) model.

21 Moreover, it can be observed that the current increase exponentially as I ≈ Vm with the increased

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1 voltage during the switching process (region C) in Fig. 3c. In the subsequent sweep from 5 to 0 V

2 (region D), the plots of ln (I) vs ln (V) can be fitted by a straight line with a slope of 1.12 (Fig. 3d),

3 suggesting that the carrier transport mechanism has probably changed to Ohmic model,

−∆Eae
I ∝ V exp( )

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4 kT (2)

∆Eae
5 where I is the current, V is the applied voltage, T is the temperature, is the activation

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6 energy of the electron, and k is Boltzmann constant. When a reverse bias is applied, the resistive

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7 state of the memory device remained at LRS, implying that the conductive paths will not change.

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9 Fig. 2. (a) The I-V curves of the RS behaviors of the Al/Au NPs:lignin/Al memory device, inset is

10 the digital photo of the testing memory device, (b) Retention test of the lignin-based memory.
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1

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2 Fig. 3. (a) The I-V curves of the Al/Au NPs:lignin/Al resistive switching memory device with

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3 different fitting models, (b) region A in the HRS, (c) region B in the HRS and region C in the

4 transaction state, and (d) region D in the LRS.

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Fig. 4 shows the surface potential energy values of the memory device with the OFF and the
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6 ON states. It can be seen that the mean surface potential increased from 338 mV to 391 mV when
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7 the device switched from OFF state to ON state. This result indicates that the Au NPs can act as
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8 trapping sites to capture the electrons [47, 48]. In addition, the surface potential of the device was
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9 stable with no obvious change after the negative bias was applied (Fig. S8 in Supporting

10 Information).
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12 Fig. 4. Surface potential energy of (a) OFF state, and (b) ON state.

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1 Based on the above data analysis, a operating mechanism of this lignin based memory is

2 represented in Fig. 5. Because the Au NPs dispersed uniformly and capped with alkali lignin in the

3 active layer, as shown in Fig. 1b, the device stays in high resistance state wthen the applied

4 voltage sweeps from 0 V to 2.75 V. With the increase of sweeping voltage from 2.75 V to 4.7 V,

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5 the Au NPs gradually block the further electrons injected from the Al electrode (Fig. 5a). The I-V

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6 curve of the device switch to obey the SCLC model [34]. Once all the traps are fully filled (Fig.

7 5b), the device switches to follow Ohmic model, indicating the electronic flow pathways are

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8 formed. Therefore, the memory device thus switches from OFF state to ON state. The WORM

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9 characteristics of this memory device can be ascribed to the following: electron traps formed
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10 between the Au NPs and the alkali lignin are deep that the captured electrons cannot escape even

11 under large reverse bias voltages [49].

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13 Fig. 5. Schematic diagram of the operating mechanism of the memory device (a) OFF state, and (b)

14 ON state.

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1

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2 Fig. 6. The Al/Au NPs:lignin/Al memory device’s switching voltage and ON/OFF ratio under
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3 different bending diameter (a) no bending, (b) 30 mm, (c) 40 mm and (d) 50 mm.
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4 The flexibilty of the memory devices were tested by bending in the convex direction. The
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5 switching voltage and ON/OFF ratio under different bending diameter were shown in Fig. 6. It can
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6 be seen that the switching voltage and ON/OFF ratio of the memory device exhibit a minor

7 fluctuations, indicating the electronic stability of devices under flexure.

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8 The enzyme degradation test of the device was carried out in DI water with proteinase K,
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9 which is an enzyme that catalyzes the hydrolysis of L-lactyl unit sequences in PLA [50]. The
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10 weight loss for pure PLA substrate and the lignin-based memory as a function of time is illustrated

11 in Fig. 7. It can be seen that the memory device shows a slightly higher degradation rate than that

12 of the pure PLA substrate at the initial stage, which is due to the alkali lignin layer dissolving in

13 the DI water and the detachment of top Al electrode from the device. Consequently, the weight

14 loss of the substrate and device increases with time after one day. However, the weight loss for the

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1 pure PLA substrate increases more significantly. This indicates that the covered bottom electrode

2 could reduce the area exposed to enzyme hydrolysis, resulting in a decrease in the weight loss.

3 After 5 days of immersion in the enzyme solution, both the device and substrate disintegrated into

4 small pieces due to serious surface erosion (Fig. 7) [51] .

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6 Fig. 7. Degradation profiles of pure PLA substrate and the memory device in enzymatic solution

7 (80 µg/ml proteinase K in DI water), insets are the photos of the memory device and PLA
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8 substrate before and after enzymatic degradation.

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9 4. Conclusion

10 Au NPs embedded alkali lignin is used as the biodegradable active layer for a write-once

11 read-many-times resistive switching memory. The active layer is easily fabricated by

12 solution-process method under normal ambient conditions in air. In addition, the ultrathin PLA

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1 film is used as a biodegradable substrate, furnishing the memory devices with good mechanical

2 support and biodegradability. The non-volatile memory based on Au NPs:alkali lignin exhibits low

3 power operation (< 5 V), large on-off ratio (~ 5 x 103) and long data retention characteristics (>103

4 s). Au NPs acting as trapping sites in the active layer are responsible for the resistive switching

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5 mechanism. The memory devices are degraded into small pieces after 5 days of immersion in

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6 proteinase K aqueous solution. This biodegradable architecture paves a way for a new breed of

7 electronics based on environmentally friendly and biodegradable materials.

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8

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9 Acknowledgements
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10 This work was supported by a grant from the City University of Hong Kong (SRG 7004377) and

11 the RGC of Hong Kong project number T42-103/16N.

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13 Appendix A. Supplementary data

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14 Supplementary data related to this article can be found online.

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Highlights:

1. Resistive switching is realized based on bio-degradable alkali lignin.

2. The active layer is fabricated on organic substrates through facile solution-process methods

under normal ambient conditions.

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3. Another bio-degradable material polylactide (PLA) film is used as an ultrathin base substrate

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endowing the memory devices with good mechanical properties.

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