The Study Report about Direct-current Triboelectric

Nanogenerators Based on Dynamic P-N Junctions

Hou Yayue, 2022

ABSTRACT

Triboelectric nanogenerators have attracted much attention these years. P-N junction is an
alternative foundation of direct-current triboelectric nanogenerator (DTENG). Sliding a P-type wafer
and a N-type wafer against each other, and if a circuit is formed, a current will occurred in the external
circuit. In this report, first, the report overviews some kinds of direct-current triboelectric
nanogenerator based on P-N junctions briefly. Second, part of the basic mechanism which is highly
related to the course will be listed. Last, there will be a summery of the application of DTENGs.

INTRODUCTION

Nanogenerator (NG) was firstly demonstrated by Z.L. Wang in 2012[1], utilizing the displacement
current in Maxwell equations.

The systematical theory has been discussed by Wang in 2017. [11] Basically, the polarization is
caused by electric filed and can be expressed by . However, Wang proposed that
polarization can also be produced by strain field as a result of piezoelectric effect and surface
contact-electrification which is independent of the presence of electric field. According to Wang,
there are two different types mechanism for nanogenerators, one is piezoelectric effect and the other
is triboelectricity. In the piezoelectric case, surface polarization charges are created due to the
strain induced ions on crystal surfaces. In the case of triboelectric nanogenerator(TENGs),
triboelectric charges are produced on surfaces simply due to a physical contact between two
different materials. Hence an addition term Ps is added to the Maxwell equations, as [11]
This equation is the fundamental to analyse the output characteristic of nanogenerators.

There are four types of TENGs, they are contact-separation mode TENG, free-standing mode TENG,
lateral-sliding mode TENG and single-electrode mode TENG.

However, for the displace current can not flow freely through the insulating dielectric materials,
the current output of TENG is limited[2]. And without the rectifying circuit, the output is alternating
current. There is another method to gain a direct-current with a high output current density straightly by
using the characteristic of diodes.

Before dynamic P-N junction, a metal/semiconductor struture has been built. A dynamic Schottky
diode has been applied as a direct current generator. By dynamically moving graphene or metal film
over Si or GaAs wafer, direct current can be generated. This novel Schottky diode is named as "moving
Schottky diode generator" . [5] However, the voltage output is less than 0.1 V, because the difference
between the Fermi-levels of semiconductor and metal is limited[5]. After that, the same team has
established a new systematic theoretical framework of dynamic P-N junction which is applied in
generator. Dynamic P-N junction is defined as a semiconductor/semiconductor structure, which moves
a N-type semiconductor on a P-type semiconductor and does not involve metal and insulating
polymeric material.[3] The first generator based on this theoretical framework was demonstrated by
involving two semiconductors with different Fermi-levels.[4] The dynamic P-N junction is different
from static P-N junction, for that majority carriers contribute to the dynamic P-N junctions but not
minority carriers in static junctions. This will be discussed later.

EXPERIMENTS AND MECHANISMS

Ⅰ. Moving Schottky Diode Generator

Fig. 1.The experiment 3D diagram

In the experiment, they pressed graphene or metal film on a semiconductor substrate. The
mechanism of the moving Schottky diode generator is based on the built-in electric field separation of
the diffusing carriers emitted by the appearance and disappearance of the depletion layer in moving
Schottky diode.[5]Actually, the generation of the current is not caused by the triboelectricity but caused
by the establishment and disapperence of Schottky junction during the movement between metal.
 Fig. 2. A normal forward bias Schottky diode in the textbook

Consider the situation of graphene film touches an N-type Si substrate. First, some basic data has
was calculated by

where Emidgap is the middle value of the band gap, k is the Boltzmann constant, T is the temperature,
ni is the intrinsic carrier concentration of the semiconductor. EF is the Fermi level of the N-type and
P-type semiconductors. [6] The electron concentration and intrinsic carrier concentration of the N-type
Si substrate used here is 4.63×1015 cm3 and 1.5×1010 cm 3 , respectively. Therefore, the Fermi level of
the P-type Si is calculated as 4.30 cm3 based on equation (1). On the other hand, the hole concentration
and intrinsic carrier concentration of the P-type Si substrate used here is 1.3×1016 cm3 and 1.5×1010
cm 3 , respectively. The conduction and valence band of P-type Si locate 4.05 eV and 5.17eV below the
vaccum energy level, respectively. Therefore, the Fermi level of the P-type Si is calculated as 4.96 eV
based on equation (2).

Actually the situation of this junction is similar to the situation in a Shottky diode in the textbook.
The N-type substrate is heavily doped and the Fermi-level of the Si is higher than the graphene which
is 4.6eV. Hence, to maintain the Fermi level change continually, charges will transfer into the graphene
which forms a built-in electric field. The current density-voltage (J-V) curves can be written according
to the thermionic emission (TE) model for a Schottky contact [7] as

e is the quantity of electron charge, V is the voltage on the diode N1F is the ideality factor, and J 0 is
the reverse saturation current density, expressed by

where A* is the effective Richardson constant of N-type Si,  barrier is the barrier height of the junction.
Based on (3) and (4) and fitting the dark current (Dark current It is referred to as reverse bias leakage
current in non-optical devices and is present in all diodes. Physically, dark current is due to the random
generation of electrons and holes within the depletion region of the device [8]) of the diode, the value
of the N1F and the  barrier can be calculated as 15.2 and 0.718eV.

Then when sliding the graphene film at a speed of 2 cm/s, a voltage output of 0.1V is observed.
When the speed increases to 4 cm/s, the output increases to 0.18V, and the maximum output can
achieve 0.22V and remain stable when the dragging speed stays at 6 cm/s. The output is related to the
sliding speed, pressed force according to different materials. The experiment result is as follows:

Fig. 3. (a) the output under different speed; (b) the output under different force;
(c) the output of different material

The researcher of this experiment proposed that the dynamic appearance and disappearance of the
depletion layer in the moving Schottky diode, which causes the separation of drifted electrons and
holes, should be the origin of the electrical power generation.[5] The drift-diffusion current can be
described as follows:

where J n , J p ,  n ,  p , Dn and D p are the electron/hole current density, the electron/hole mobility, and the
electron/hole diffusion coefficient in semiconductor, respectively. U is the potential, d is the distance
of the built-in electric field, e is the elementary charge, and n and p are the position-dependent electron
density and hole density in semiconductor.

When the graphene or metal film contact the Si substrate, a depletion region will form at the
interface of the junction immediately. And when the film sliding, the end of the film will leave the
contact area which leads to the disappearance of depletion region and the front part of the film will
contact new area of substrate and re-establish the depletion region at the front part of the junction. The
whole contact area remains static. However, the process of the disappearance and re-establish of the
depletion region will break the static distribution and accelerate or bound back the electrons and holes
which are diffusing across the depletion region. The output current is caused by the electrons emitted
because of the change of the depletion region. The direction of the current is determined by the work
function of two materials and the direction of the built-in electric field. If the built-in electric field is
from semiconductor to metal, the electrons above the work function of the semiconductor will transfer
to the semiconductor while forming the built-in field. And the diffusing current transfer to metal from
semiconductor and cause a output current.[5]

As for the transform of the energy, there is some other explains about the moving Schottky diode
model. The mechanism for DC is that frictional energy released from forming of atomic bonds excites
electron–hole pairs in semiconductor side and dynamic electron in metal side, which are directionally
separated under the built-in electric field. [9] Another explain is the electron from the metal side can
transit to the unoccupied surface states at the semiconductor side, and the energy released could
stimulate the tunneling/transition of electrons from the metal side to the semiconductor side.[10]

Ⅱ. Dynamic P-N Junction generator

This kind of generator is a little bit same as the moving Schottky diode generator. A N-type
semiconductor is sliding on a P-type semiconductor linearly and circularly. Take N-GaAs and P-Si as
example, for these two materials have the best rectification characteristic[3].

Fig. 4. (a) the 3D diagram for the experiment; (b) the hole harvest device; (c) the path of electrons and holes

In the front part of the dynamic P-N junction, the electrons and holes will diffuse to P-type and N-type
semiconductors, establishing the built-in electric field. In the rear part of the dynamic P-N junction, the
diffusing electrons/holes will lose their path for diffusing and then are reflected by the built-in field. In
a P-N junction there is a balance above the depletion region. The diffusing and the drift current is
opposite and against each other. But the separation of the interface breaks the balance between
diffusing current and drifted current. the electric field is still exist but the diffusion current was
interrupted and will be bound back in the opposite direction, thus the output has been generated.[4] The
path of the electrons and holes are shown in Fig.4.(c), for the bound back carriers which actually causes
the output current are majority carriers, hence the dynamic current is majority carrier induced.

Fig. 4. (a) the output of different material; (b) the output of P-Si/N-GaAs; (c) the output under different contact area

The experiment about this kind of generator has been taken by the team of Zhejiang University[3] .
The experiment contains three different kinds of P-N junctions which are P-Si/N-Si, P-Si/N-GaN and
P-Si/N-GaAs. Among those three materials, the output voltage of P-Si/N-GaAs is the largest. If the
N-type GaAs wafer was pressed on the P-type Si substrate compactly with a 6N force, which showed
typical rectification behavior with a low leakage current density of 1.5 µA/cm2 under the bias voltage
of -3 V as shown in Fig.5.(b), The work function of N-type GaAs and P-type Si used here is 4.10 eV
and 5.12 eV , respectively. Accordingly, the work function of N-GaAs is smaller than P-Si, thus a
built-in electric field will be formed between the N-GaAs and P-Si substrate. When the N-type GaAs
was dragged along the surface of the P-type Si the maximal output voltage is up to 0.7 V.
 When test films with different area, the output current increases linearly, and the current density
almost remains constant. This means the ability of unit area to generate output current is independent
from contact area. Shown in Fig.5.(c).

The experiment result will be discussed in quantity based on the Possion equation. The Poisson
equation is the basic equation for describing the electrostatic behavior of charges:[12]

The electron and holes current can be written as follows,

where J n and J p are the electron and hole current densities, e is the value of the unit electronic charge,
 n and  p are the electron and hole mobilities, n and p are the concentrations of free electrons and
free holes, Dn and Dp are the diffusion coefficients for electrons and holes, E is the electric field. If
separate the diffusion and drift current, the current density can be writtren as follows,

where J ndrift , J ndiff , J drift

p , J diff
p are the drift and diffusion current density of electron and holes,  n ,  p are
the electron and hole mobility, Dn , D p are the electron diffusion coeffificient of GaAs and Si,
respectively. E is the built-in electric field, e is the elementary charge, n, p are the position-dependent
electron and hole density in GaAs or Si. When the GaAs wafer moves along the Si substrate, there is a
dynamic process of disappearing of the depletion layer in the rear end and the re-establishment of the
depletion layer in the front end. In micro scale, the effective working area of the dynamic P-N junction
is assumed as the contact area of the GaAs wafer and Si substrate during the movement, which remains
unchanged. However, the dynamic process of the generation and disappearance of the depletion layer
in the dynamic GaAs/Si junction will break up the static carrier distribution equilibrium. The
destruction of the P-N junction will narrow down the space charge region and reflect the space
electrons/holes, which is equivalent to capacitance discharge process.

APPLICATIONS

Actually there are already so many applications based on TENGs. As reviewed in Wang's paper in
2021[10], TENGs can be used as micro- and nano- power sources, self-power sensors, blue energy
harvesting, high voltage sources, scanning probe for measuring interface charges and hybridized NGs.

N.Y.Tasneem has designed a self-powered motion sensor based on reverse-electrowetting on

dielectric (REWOD) energy harvesting having the capability of remotely keeping a track of any motion
activity. The energy harvester includes a rectifier and a voltage regulator to provide the DC supply
voltage to the analog front-end and the transmitter to wirelessly transfer the data from the motion
sensor. [13] Lin.Z.H. has proposed a self-powered photodetector based on triboelectric nanogenerator
(TENG) configuration. 3D dendritic TiO2 nanostructures are synthesized as the built-in UV
photodetector as well as the contact material of the TENG. [14] In He Q.R.'s paper, a p-n junction ZnO
textile nanogenerator is successfully fabricated on conductive textiles utilising PEDOT:PSS/CuSCN
-coated ZnO nanorods, combining the advantage of ZnO piezoelectricity and textile flexibility. [15]

CONCLUSION

This paper has talked about the sliding mode TENGs and listed two typical types of sliding mode
generator.One is based on Schottky diode and the other is based on dynamic P-N junctions. The paper
has illustrated the experiment of establishing these two kinds of DTENGs and analysis the basic
mechanism of the two DTENG models.

Generally speaking, the moving Schottky diode generator and the dynamic P-N junction generator
are all related to the discharge and re-establishment of the depletion region. When the metal or
semiconductor film sliding on the substrate, the depletion in the rear part of the film will be broken and
the new depletion region will form in the front part of the film. For Schottky diode, the current is
caused by the emitted electrons because of the separation of diffusion and drift current. For dynamic
P-N junctions. the output current is caused by the broken balance of diffusing and drift current, the
diffusing electrons and holes will be bound back and accelerated by the built-in electric field which
causes the observed current in the external circuit.

Though there has been already several applications on DTENGs, the future of the DTENGs is still
promising.

REFERENCES

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