S1

Supporting Information for

Robust DNA-bridged memristor for textile chip

This file includes:

Methods (Pages S2-S4)

Supplementary Figures 1 to 17 (Pages S5-S21)

Supplementary Tables 1(Page S22 )

Supplementary References (Pages S23-S24)

S2

1. Preparation of DNA solution

The preparation of DNA solution followed the previous report.[1] 10 mg

deoxyribonucleic acid sodium (ss-DNA,99%, Sigma-Aldrich) was dissolved in 5 mL

deionized water and sonicated for 30 min. Then, hexadecyltrimethylammonium

chloride (CTMA, 99%, Makun) was added to the DNA solution, maintaining a

DNA/CTMA weight ratio of 1/1. The resulting solution was sonicated for 30 min. The

production was centrifuged at 8000 rpm for 5 min, and the supernatant was discarded

and the precipitate was collected to be re-dispersed in n-butanol.

2. Deposition of DNA on Ag or Pt fibres through electrophoretic deposition

Two Ag fibers (99.99%, 50 μm, Alfa Aesar) or Pt fibers (99.99%, 50 μm, Alfa Aesar)

were connected to a direct current supply (Keithley 2400 Source Meter) and dipped into

the as-prepared solution. Depending on the time or the voltage applied, the film

thickness was controlled. A voltage of 1.8 V and a period of 3 min had been chosen

after careful experimental optimization.

3. Preparation of modified photoanode fiber

First, a Ti fiber (99.99%, 127 μm, Alfa Aesar) was sequentially sonicated by de-ionized

water, acetone and isopropanol each for 5 min, followed by anodic oxidation in a water

bath at 50 oC. Then, a mixture solvent of water and glycerol (volume ratio, 1/1)

containing 0.27 M NH4F was used as the electrolyte. The growth was operated in a two-

electrode system with a Ti fiber and a Pt plate as the anode and cathode at 20 V for 7

min, respectively. The resulting Ti fiber was washed by de-ionized and annealed at 500 oC for 60 min.

4. Preparation of aligned CNT sheet and fiber

CNT sheet was dry-drawn from spinnable CNT array synthesized by chemical vapor

deposition.[2] Al2O3 (3 nm) and Fe (1.2 nm) were deposited on silicon wafer by electron

beam evaporation as the catalyst. Ethylene (90 sccm), Ar (400 sccm) and H2 (30 sccm)

were used as carbon source, carrier gas and reduction gas, respectively. The spinnable

CNT array was grown at 750 °C in a quartz tube furnace for 10 min. CNT fiber was

prepared by further twisting the aligned CNT sheet.[3, 4]

5. Fabrication of fiber-shaped all-inorganic perovskite solar cell

The CsPbBr3 quantum dots were synthesized according to the previous literature.[5] A

modified photoanode fiber was dip-coated in the CsPbBr3 QDs solution and annealed

S3

at 300 oC, transforming QDs to large CsPbBr3 crystals and removing organic ligands.

This process was repeated for 20 to 100 times to obtain different thicknesses of active

layers. Finally, the aligned carbon nanotube sheet as the counter electrode was wrapped

onto the composite fiber to obtain a fiber-shaped all-inorganic perovskite solar cell. The

carbon nanotube (CNT) sheet was obtained from a spinnable CNT array synthesized by

chemical vapour deposition.

6. Fabrication of fiber-shaped Ni/Bi full battery[6]

A rGO/Bi/CNT hybrid fiber anode was first prepared. The rGO/Bi composite was

electro-co-deposited on the CNT fiber in a solution (40 mL) containing graphene oxide

(0.03 mg/mL), ethylenediaminetetraacetic acid disodium salt (EDTA·2Na, 0.1 M) and

Bi(NO3)3·5H2O (50 × 10−3 m). Carbon rod and Hg/HgO electrodes were used as counter

and reference electrodes, respectively. A potential of −1.2 V versus Hg/HgO electrode

was applied for 60 s. After electrodeposition, the sample was washed with water and

dried at 80 °C. Finally, the sample was dipped in graphene oxide solution (1.5 mg/mL)

for ten times and dried at 80 °C in air.

A rGO/Ni/NiO/CNT fibre cathode was then prepared. 12 mg of the rGO/Ni/NiO hybrid

was dispersed in 2 mL ethanol by ultrasonication at 60 °C for 10 min, followed by

immersion of eight stacked CNT sheets and later scrolled into an rGO/Ni/NiO/CNT

hybrid fibre.

The fiber‐shaped Ni//Bi battery can be finally fabricated. The rGO/Bi/CNT and

rGO/Ni/NiO/CNT fiber electrodes were twisted with a separator between them and then

inserted into a poly (tetrafluoroethylene) tube. After an electrolyte was injected into the

tube, both ends of the tube were sealed.

7. Fabrication of fiber-shaped light-emitting device

The ZnS:Cu and polydimethylsiloxane mixture was prepared by mixing

polydimethylsiloxane precursor, namely, a mixture of elastomer prepolymer and curing

agent with a weight ratio of 9/1, and ZnS:Cu microparticles at a weight ratio of 1/1.

Next, the obtained mixture was dip-coated onto a silver-plated nylon yarn (100 μm in

diameter) and then cured in the oil bath for 10 s at 160 oC. The obtained composite fiber

was washed with ethanol and then dried at 80 °C for 30 min. After that, an enamelled

copper fiber was spirally wound onto the resulting composite fiber to fabricate a fiber-

S4

shape light-emitting device.

8. Integration

The fiber-shaped perovskite solar cells were connected in series with fiber-shaped Ni/Bi

batteries and worked as the power supply for the computing unit. The direct current

voltage would be transformed into sweep pulses via a commercial transformer and

provided tunable pulse intensity (e.g., +0.2V, +0.4V and -0.2V).

9. Electrical measurements and characterizations

The electrical measurements of the memristors including direct current, pulse electrical

measurements and basic logic gates measurements were performed in the atmosphere

using semiconductor characterization system (Keithley 2400 and Agilent B1500 with

pulse generator unit). As for the memristor, the Pt fibers (99.99%,0.025 mm, Alfa Aesar)

were carefully interlaced with the Ag fibers coated with DNA. The Ag electrode was

applied with an external bias while the Pt electrode was kept as ground.

J–V curves of the fiber-shaped all-inorganic perovskite solar cell were recorded by a

Keithley 2400 Source Meter under the illumination (100 mW cm-2) of a simulated

AM1.5 solar light from a solar simulator (OrielSol3A 94023A equipped with a 450 W

Xe lamp and an AM1.5 filter). Current-voltage and galvanostatic charge/discharge

measurements were conducted using an electrochemical workstation (CHI 660D). The

light intensity of the fiber-shaped light-emitting device was carried out by a

Photoresearch PR-680 under an alternating current waveform using a function

generator (3312 A; Hewlett Packard) and a high-voltage amplifier (610 D; TREK Inc.).

The morphologies were characterized by field-emitting scanning electron microscopy

(Hitachi S-4800) and high-resolution transmission electron microscopy (JEOL, JEM-

2100F). The chemical composition and structure were confirmed by Fourier transform

infrared spectroscopy (Nicolet 6700) and laser Raman spectroscopy (XploRA). The

orientation of the DNA molecules was characterized by grazing incidence small angle

scattering (Xeuss2.0). Plan-view conductive filament mapping was characterized by

conducting atom force microscopy (Multimode V, Bruker Nano Surfaces) and Cr/Pt-

coated tips (Multi75E-G, Budget Sensors).

S5

Figure S1. Schematic illustration to DNA assembly via electrophoretic deposition with

simultaneous modification of Ag nanoparticles (AgNPs).

S6

Figure S2. Raman spectra of the DNA/AgNPs film prepared via electrophoretic

deposition.

S7

Figure S3. High-resolution cross-sectional transmission electron microscopy images

of the DNA/AgNP film prepared via electrophoretic deposition. Scale bars in a and b,

5 nm and 1 nm, respectively.

S8

Figure S4. X-ray photoelectron spectroscopy of the DNA/AgNP film prepared via

electrophoretic deposition.

S9

Figure S5. Capacitance–voltage characteristics of the DNA assembly process via

electrophoretic deposition with different electrodes. a) Platinum. b) Silver.

S10

Figure S6. Fourier transform infrared spectra of the DNA/AgNP layer.

S11

Figure S7. a) Schematic illustration of conducting atomic force microscopy test

method and plan-view conductive filament mapping by conductive atomic force

microscopy. b) Under set state. c) Reset state.

S12

Figure S8. Switching speed of the Pt/DNA/Ag memristor with homogeneously

distributed DNA prepared via dip coating.

S13

Figure S9. Small-area Fourier transform infrared spectra of the Pt/DNA/AgNPs/Ag

memristor prepared via electrophoretic deposition under original and set states.

S14

Figure S10. Scanning electron microscopy images of DNA assembly via

electrophoretic deposition with Pt electrode at increasing magnifications from left to

right. Scale bars in a, b and c, 10 μm, 1 μm and 200 nm, respectively.

S15

Figure S11. Current-voltage characteristics of the Pt/DNA/Ag memristor (inset is the

schematic illustration of the device structure).

S16

Figure S12. a) Fabrication process of fiber-shaped perovskite solar cell. b-d)

Corresponding scanning electron microscopy images in a. Scar bars in b, c and d, 200

nm, 200 nm and 5 μm, respectively.

S17

Figure S13. Current-voltage characteristic of the fiber-shaped solar cell.

S18

Figure S14. a) Fabrication process of fiber-shaped Ni/Bi full battery. b-c) Scanning

electron microscopy images of rGO/Bi/CNT fiber anode at low and high magnification,

respectively. d-e) Scanning electron microscopy images of rGO/Ni/NiO/CNT fiber

cathode at low and high magnification, respectively. Scale bars in b, c, d and e, 20 μm,

2 μm, 20 μm and 200 nm, respectively.

S19

Figure S15. a) Galvanostatic charge and discharge profiles of fiber-shaped Ni/Bi full

battery. b) Cycling performance for 10,000 cycles.

S20

Figure 16. a) Schematic diagram for the fabrication of electroluminescent fiber. b-d)

Corresponding Scanning electron microscopy images in a. Scale bars in b-d, 100 μm.

S21

Figure S17. a) Cross-sectional scanning electron microscopy image of the light-

emitting fiber. b-c) Luminescent properties under different bias and frequencies,

respectively. d) Photographs of the flexible light-emitting fiber under different bending

or twisting conditions. Scale bars in a and d, 100 μm and 1 cm, respectively.

S22

Supplementary Table 1. Comparison of the memristive performances of this work with the state-of-art organic memristors.

Device structure Set (V) Reset (V) Set power/reset

power (W) Retention time (s) On/off

Cycle

number (n) Reference

Ag/DNA:AgNPs/Pt 0.20.4 -0.05-0.2 10-10

/10-5

105 10

6 1000 This work

Al/GO–PVK/ITO -2 4 / 104 10

3 / [7]

Au/PI:PCBM/Al 3 -4 10-5

/10-2

104 10

3 300 [8]

ITO/RGO‐PFCF/Al -1.2 2 / 104 10

2 / [9]

Au/Co(III) polymer/Au -5 5 / 104 102 / [10]

Ag/PI/GO:PI/PI/ITO 2.54.5 -7 10-7

/10-3

1.6×103 10

3 130 [11]

Ag/(PAH/ferritin)15

/pt -1.5 2 10-3

/10-1

One year 102 300 [12]

Al/silk/ITO 14 -14 / 120 11 1000 [13]

Ag/sericin/Au 2.5 -0.5 10-7

/10-2

103 10

6 300 [14]

ITO/Al-chelated gelation/ITO -1.0 1.8~2.6 10-5

/10-1

105 10

4 60 [15]

Al/PVK/ITO 1 -3.1 10-4

/10-1

104 10

3 / [16]

Ag/WK@AuNCs–SF/ITO 0.4 -0.2 10-5

/10-3

1.4×104 10

2 100 [17]

Au/lignin/ITO/PET -0.5-0.7 0.50.7 10-4

/10-4

/ / 10 [18]

ITO/mer-

[Ru(L)3](PF

6)2:AuNc/ITO

0.490.55 -0.51-0.59 10-10

/8×10-7

3×106 10

310

5 10

12 [19]

Au/PS:PCBM/Al 3.04.0 -4 10-7

/10-2

104 10

3 500 [20]

Al/S-layer protein (Slp)/ITO 8 -8 10-3

/10-3

4×103 6.2 500 [21]

Ag/2DPBTA+PDA

/ITO 0.9 3 10-7

/10-3

3.6×104 10

5 200 [22]

S23

Supplementary References

[1] J. Nizioł, J. Fiedor, J. Pagacz, E. Hebda, M. Marzec, E. Gondek, I. V. Kityk, J.

Mater. Sci. Mater. Electron. 2017, 28, 259–268.

[2] Z. Yang, T. Chen, R. He, G. Guan, H. Li, L. Qiu, H. Peng, Adv. Mater. 2011, 23,

5436–5439.

[3] X. Fu, Z. Li, L. Xu, M. Liao, H. Sun, S. Xie, X. Sun, B. Wang, H. Peng, Sci. China

Mater. 2019, 62, 955-964.

[4] Y. Hong, X. Cheng, G. Liu, D. Hong, S. He, B. Wang, X. Sun, H. Peng, Chinese J.

Polym. Sci. 2019, 37, 737-743.

[5] J. Song, J. Li, L. Xu, J. Li, F. Zhang, B. Han, Q. Shan, H. Zeng, Adv. Mater. 2018,

30, 1800764.

[6] M. Wang, S. Xie, C. Tang, Y. Zhao, M. Liao, L. Ye, B. Wang, H. Peng, Adv. Funct.

Mater. 2019, 30, 1905971.

[7] G. Liu, X. Zhuang, Y. Chen, B. Zhang, J. Zhu, C. X. Zhu, K. G. Neoh, E. T. Kang,

Appl. Phys. Lett. 2009, 95, 253301.

[8] B. Cho, T. W. Kim, S. Song, Y. Ji, M. Jo, H. Hwang, G. Y. Jung, T. Lee, Adv.

Mater. 2010, 22, 1228–1232.

[9] B. Zhang, G. Liu, Y. Chen, L. J. Zeng, C. X. Zhu, K. G. Neoh, C. Wang, E. T.

Kang, Chem. A Eur. J. 2011, 17, 13646–13652.

[10] A. Bandyopadhyay, S. Sahu, M. Higuchi, J. Am. Chem. Soc. 2011, 133, 1168–

1171.

[11] C. Wu, F. Li, Y. Zhang, T. Guo, T. Chen, Appl. Phys. Lett. 2011, 99, 042108.

[12] Y. Ko, Y. Kim, H. Baek, J. Cho, ACS Nano 2011, 5, 9918–9926.

[13] M. K. Hota, M. K. Bera, B. Kundu, S. C. Kundu, C. K. Maiti, Adv. Funct. Mater.

2012, 22, 4493–4499.

[14] H. Wang, F. Meng, Y. Cai, L. Zheng, Y. Li, Y. Liu, Y. Jiang, X. Wang, X. Chen,

Adv. Mater. 2013, 25, 5498–5503.

[15] Y. C. Chang, Y. H. Wang, Appl. Phys. Lett. 2015, 106, 123302.

[16] H. F. Ling, M. D. Yi, M. Nagai, L. H. Xie, L. Y. Wang, B. Hu, W. Huang, Adv.

Mater. 2017, 29, 1701333.

[17] Y. Xing, C. Shi, J. Zhao, W. Qiu, N. Lin, J. Wang, X. B. Yan, W. D. Yu, X. Y.

Liu, Small 2017, 13, 1702390.

[18] Y. Park, J. S. Lee, ACS Nano 2017, 11, 8962–8969.

[19] S. Goswami, A. J. Matula, S. P. Rath, S. Hedström, S. Saha, M. Annamalai, D.

S24

Sengupta, A. Patra, S. Ghosh, H. Jani, et al., Nat. Mater. 2017, 16, 1216–1224.

[20] W. Lee, Y. Kim, Y. Song, K. Cho, D. Yoo, H. Ahn, K. Kang, T. Lee, Adv. Funct.

Mater. 2018, 28, 1801162.

[21] A. Moudgil, N. Kalyani, G. Sinsinbar, S. Das, P. Mishra, ACS Appl. Mater.

Interfaces 2018, 10, 4866–4873.

[22] J. Liu, F. Yang, L. Cao, B. Li, K. Yuan, S. Lei, W. Hu, Adv. Mater. 2019, 31,

1902264, 1–7.