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Synthesis, surface properties, crystal structure and dye-sensitized solar cell per-
performance of TiO2 nanotube arrays anodized under different parameters

Zao Yi, Yu Zeng, Hui Wu, Xifang Chen, Yunxia Fan, Hua Yang, Yongjian
Tang, Yougen Yi, Junqiao Wang, Pinghui Wu

PII: S2211-3797(19)32051-0
DOI: https://doi.org/10.1016/j.rinp.2019.102609
Reference: RINP 102609

To appear in: Results in Physics

Received Date: 7 July 2019

Revised Date: 9 August 2019
Accepted Date: 20 August 2019

Please cite this article as: Yi, Z., Zeng, Y., Wu, H., Chen, X., Fan, Y., Yang, H., Tang, Y., Yi, Y., Wang, J., Wu,
P., Synthesis, surface properties, crystal structure and dye-sensitized solar cell performance of TiO2 nanotube
arrays anodized under different parameters, Results in Physics (2019), doi:
https://doi.org/10.1016/j.rinp.2019.102609

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 Synthesis, surface properties, crystal structure and

dye-sensitized solar cell performance of TiO2 nanotube arrays

anodized under different parameters

Zao Yi 1,3, Yu Zeng 1, Hui Wu1, Xifang Chen 1,3, Yunxia Fan 1,3, Hua Yang 2, Yongjian Tang 3,

Yougen Yi 4, Junqiao Wang 5, and Pinghui Wu 6

1 School of Science, Southwest University of Science and Technology, Mianyang 621010, China

2 State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou

University of Technology, Lanzhou 730050, China

3 Sichuan Civil-Military Integration Institute, Mianyang 621010, China

4 College of Physics and Electronics, Central South University, Changsha 410083 China

5 School of Physics and Engineering and Key Laboratory of Materials Physics of Ministry of

Education of China, Zhengzhou University, Zhengzhou 450001, China

6
Research Center for Photonic Technology, Key Laboratory of Information Functional Material for

Fujian Higher Education, Quanzhou Normal University, Fujian 362000, China

 Correspondence should be addressed to Pinghui Wu

Tel: 86-0595-22003815; Fax: 86-0595-22003815

E-mail address: phwu@zju.edu.cn

1
Abstract

In this paper, TiO2 nanotube arrays were prepared by anodic oxidation method. The effects of water

content, anodizing time and sample post-treatment on the morphology and crystal structure of TiO 2

nanotube arrays were systematically investigated. We explored the performance of dye-sensitized solar

cells (DSSCs) based on dye N-719. The TiO 2 nanotube arrays prepared under different water content

and different anodizing time conditions were used as photoanodes. The results show that DSSC has

best photovoltaic performance when the water content is 2 vol%. With the increase of oxidation time,

Jsc increases continuously, open voltage (Voc) and fill factor (FF) increase first and then decrease. The

best optoelectronic properties obtained that the short circuit current, open circuit voltage, fill factor and

photoelectric conversion efficiency as following, J sc = 5.2 mA / cm 2 , Voc = 0.7 V, FF = 0.54, η= 1.96%

respectively.

Keywords: TiO2 Nanotube Arrays; Anodic Oxidation Method; Water content; Anodizing time; Dye-

sensitized Solar Cell (DSSC)

1. Introduction

As an important wide bandgap semiconductor functional material, TiO 2 has been applied in many

fields due to its advantages such as high oxidation activity, non-toxicity, environmentally friendly,

good chemical stability, good corrosion resistance and low-cost material [1-3]. In recent years, with the

rapid development of nanotechnology, TiO2 has been prepared into nanomaterials of various forms,

such as TiO2 nanorods, TiO2 nanoparticles and TiO2 nanotubes [4-6]. Compared with other forms of

TiO2 nanomaterials, TiO2 nanotubes, as a special form of nano TiO 2, have attracted people's attention

due to its excellent properties such as high aspect ratio, high specific surface area and efficient electron

2
transport channel [7]. TiO2 nanotubes have important development prospects in photocatalysis, sensors

and solar cells [8-13] due to their special properties.

There are many methods for preparing TiO2 nanotube arrays. At present, the methods used

commonly are hydrothermal synthesis, template synthesis method, and anodic oxidation [14-16]. The

anodic oxidation is a typical electrochemical process to fabricate titania nanotubes in which a pure

titanium sheet is used as an anode, and an oxidation process is performed by energization in a suitable

electrolyte [17]. At the same time, the length, the diameter, the wall thickness and the shape of the

nanotubes can be controlled by adjusting the parameters such as anodizing time and electrolyte system

in the whole electrochemical process [18-20]. In this method, the TiO 2 nanotubes grown directly on Ti

sheet can be tightly bonded to the titanium metal itself. In addition, titanium has strong corrosion

resistance. Therefore, the TiO2 nanotubes prepared by using titanium as the matrix in the anodic

oxidation method are more conducive to the preparation of nanodevices [21-23]. Compared with other

preparation methods, the anodic oxidation method has the advantages of low cost and simple

preparation process. The prepared TiO2 nanotube arrays are arranged neatly and have high stability

[24].

Dye-sensitized solar cell is based on photoanodes which are wide band gap oxides such as TiO 2,

ZnO, SnO2 and etc [25-27]. It is prepared by dye sensitization, transition metal ion doping sensitization

or inorganic narrow band gap semiconductor sensitization and other methods [28]. DSSC is more

promising for commercialization than other solar cells due to its advantages such as low preparation

cost, light weight of materials, good processing performance and large design space of compound

structure [29-31]. At present, a porous TiO2 thin films is usually used for preparing a DSSC

photoanode. Simultaneously, preparation of one-dimensional nanomaterials has the following three

3
advantages: i) Increasing the specific surface area by reducing the nanotube diameter and increasing

the tube length - the titanium dioxide nanotubes with large specific surface area are beneficial to the

effective adsorption of low absorption coefficient dyes (such as the N-719 dye we used in this study)

[32]. ii) A good electrical contact is formed between the materials to reduce the composite loss during

electron transport, resulting in higher VOC [33]. iii) The one-dimensional materials extend electron

lifetime, thus producing a larger JSC [34, 35].

In this paper, the TiO2 nanotube arrays were prepared by anodic oxidation method. We controlled

the water content and the anodizing time during the anodization process and the post-treatment of the

sample. The morphology and crystal structure of the prepared TiO2 nanotube arrays were characterized

and analyzed by FETEM, SEM and XRD to understand the effects of various process parameters on

the arrays. And then the TiO2 nanotube arrays obtained under different processes were N-719 dye-

sensitized. Finally, they were assembled into dye-sensitized solar cells as photoanode, and the

photoelectric properties of the dye-sensitized solar cell were tested and analyzed.

2. Experimental

2.1. Reagents and materials

Titanium foil (99.99%, China New Metal Materials Technology Co., Ltd.); platinum electrode

(Tianjin Ida Hengsheng Technology Development Co., Ltd.); electrolytic cell (polytetrafluoroethylene,

ZHENJIANG REALS MACROMOLECULAR MATERIAL Co., Ltd.); ethylene glycol (EG, AR,

Tianjin Kemiou Chemical Reagent Co., Ltd.); ammonium fluoride (NH 4F, 96%, Alfa Aesar (China)

Chemical Co., Ltd.); acetone (C3H6O, AR, Tianjin Kemiou Chemical Reagent Co., Ltd.); anhydrous

ethanol (C2H6O, AR, Tianjin Kemiou Chemical Reagent Co., Ltd.); (I 2, 99.99%, Alfa Aesar (China)

Chemical Co., Ltd.); 4-tert-butylpyridine (TBP, Tianjin Kemiou Chemical Reagent Co., Ltd.);

4
guanidinium thiocyanate (GuNCS, 99%, Alfa Aesar (China) Chemical Co., Ltd.); 1,2-dimethyl-3-

Propyl imidazolium iodide (DMPⅡ, 99%, Alfa Aesar (China) Chemical Co., Ltd.); N-719 dye

(Yingkou OPV TECH New Energy Co., Ltd.); acetonitrile (AN, 99%, Tianjin Kemiou

Chemical Reagent Co., Ltd.); lithium iodide (LiI , 99.99%, Alfa Aesar (China) Chemical Co., Ltd.);

heat sealable film (60μm, 99%, Dalian QiSeGuang solar technology development Co., Ltd.); platinum

plating FTO (12×18mm, Dalian QiSeGuang solar technology development Co., Ltd.).

2.2. Preparation of TiO2 nanotube arrays by anodic oxidation method

High-purity titanium foil (the area of 15×25 mm2, the thickness of 0.25 mm) was ultrasonically

cleaned with acetone and anhydrous ethanol and deionized water for 15 minutes respectively.

(Ultrasonic cleaner (KQ-50D, Shanghai Binengxin Ultrasonic Co., Ltd.)) Then, dried with nitrogen gas

and sealed one side of the titanium foil with insulating tape. The titanium foil was connected to the

anode, and the area of the platinized electrode is 15×15 mm2. The two electrodes were opposite, and

the spacing is 4 cm. In the reaction process, the effective area of titanium foil is 15×15 mm 2. The

electrolyte was prepared with EG, NH4F and deionized water. Various anodizing times and water

contents were applied to change the morphology and crystal structureof TiO 2 nanotube arrays. The

experiment was carried out at room temperature (20 ℃) with magnetic stirring. After the reaction, we

removed the titanium foil, took off the insulation glue on the back of the titanium foil, used anhydrous

ethanol and deionized water respectively sonicating for 5 min, and then blow dried with nitrogen for

later use.

2.3. Preparation of Dye-sensitized Solar Cells

In the preparation of DSSC, the prepared TiO 2 nanotube array film sample was heated to 100 °C,

completely immersed in the 0.3 mM N-719 dye solution (anhydrous ethanol was used as solvent),

5
sealed, protected from light for 24 h, and taken out. The unadsorbed dye was rinsed with absolute

ethanol, and the sample was blown dry with nitrogen. The platinized layer was prepared on FTO

conductive glass by screen printing technology. The area of conductive glass is 12×18 mm, and the

effective area of platinum film is 7×7 mm 2. The conductive glass has a thickness of 2.2 mm and a light

transmittance of more than 90%. The sensitized photoanode was placed face to face with the Pt counter

electrode with a 60 μm heat seal film interposed between the two as a gap. Next, the fixed sample was

heated in an oven at 120 °C for 1 minute to thermally fix the heat seal film between the two electrodes.

After that, the electrolyte solution was dropped into the small hole with a syringe. The concentrations

of LiI, I2, DMPII, GuNCS and TBP in the electrolyte solution were 0.3 mol•L -1, 0.03 mol•L-1, 0.6

mol•L-1, 0.1 mol•L-1 and 0.5 mol•L-1 respectively. The electrolyte solution was uniformly diffused

between the two electrodes and fills the entire battery, and the small holes were sealed with a small

amount of glue.

2.4. Performance Measurement of Dye-sensitized Solar Cells

In this experiment, the J-V curve of the dye-sensitized solar cell was recorded by the K2400 source

meter (K2400, Keithley, USA). The effective area of DSSC assembled in the experiment is 0.7×0.7

cm2. The incident light source is a full-spectrum sunlight simulator (LOT, Quantum Scientific

Instruments Trading (Beijing) Co., Ltd. - Quantum Design China subsidiary). The incident light

intensity is 1.5 sunlight, i.e. 100mW•cm -2. Prior to testing, the sunlight simulator was calibrated with

standard solar cells (HG-SSC, Beijing Heng Gong Instruments Co., Ltd.). Since the TiO 2 nanotube

array prepared by the anodic oxidation method was grown on the titanium foil, and the titanium foil

itself is not transparent, the entire photoanode is opaque. Therefore, during the test, the incident

sunlight must be from the counter electrode.

6
2.5. Characterization

The morphology and crystal structure of the samples were investigated by scanning electron

microscopy (SEM, JSM-6390LV, Japan) and X-ray diffraction. X-ray diffraction (XRD) measurement

are performed using a D/max 2550 VB +, Japanese Rigaku. Cu target Kα λ=0.154056 nm, scanning

range of 20°~ 80° with the minimum step of 0.02 °, and the scanning rate of 5 °/min. The

microstructure and characteristics of the samples were observed using the FETEM (Tcneai G2 F20,

USA).

3. Results and Discussions

3.1. The Reaction Mechanism of TiO2 Nanotube Arrays Prepared by Anodic Oxidation Method

In the fluorine-containing organic electrolyte system, the process of preparing TiO2 nanotube arrays

by anodic oxidation mainly includes the following four reactions:

H2O →2H + + O2 -
(1-1)
-
Ti → Ti4 + + 4e (1-2)
Ti4 + + 2O2 - →TiO2 (1-3)
-
-
TiO2 + 6F + 4H + → [TiF6] + 2H (1-4)
O 2

The entire anodic oxidation process includes the following three stages:

Primary Stage: this stage is mainly the formation of TiO 2 barrier layer. After the start of the reaction,

the water concentrated in the vicinity of the anode is rapidly ionized by the electric field to produce O 2-

( formula ( 1 - 1 ) ). At the same time, the titanium foil at the positive electrode ( anode ) of the power

supply is rapidly dissolved into Ti 4+ ions ( formula ( 1 - 2 ) ). Under the action of an electric field, a

large amount of Ti4+ ions rapidly combine with oxygen-containing ions in the electrolyte to generate

TiO2 ( formula ( 1 - 3 ) ). Therefore, a dense TiO2 film will be formed on the surface of the titanium

foil.
7
 Second Stage: this stage is the initial stage of the formation of the porous layer. The electric field

strength of the TiO2 film layer is rapidly enhanced with the formation of the TiO 2 film on the surface of

the titanium foil. The F- in the solution reacts with the produced TiO2 to form a soluble [TiF6]-(formula

(1-4)) dissolved in the electrolyte. Due to the volume increase caused by the formation of oxide film,

internal stress is formed in the oxide layer. Due to the uneven distribution of internal stress, the

chemical etching of the F- doped oxide film is not uniform, and a large number of small depressions are

formed on the surface of the oxide layer. Subsequent holes are formed on the basis of these tiny

depressions [36].

The Third Stage: this stage is the stable growth of the porous membrane. In the initial stage of

growth of the nanoporous to the titanium matrix, unoxidized metal titanium remains between the

porous. As the holes extend, the electric field strength of these metal regions increases, so the growth

rate and dissolution rate of the oxide film under the electric field support also accelerates. At the same

time, stress corrosion between adjacent nanoporous creates gaps at the interface of the holes. The

barrier layer at the bottom of TiO2 continuously pushes towards the titanium matrix, resulting in the

hole extending continuously. When the dissolution rate of the oxide layer at the bottom of the hole is

equal to the advancing rate of the barrier layer/ metal interface, the hole will continue to extend, but the

thickness of the barrier layer will remain the same. In this process, as with the growth process of the

nanoporous, the junction between the holes continues to extend toward the titanium matrix, eventually

forming the tube wall [37].

Finally, when the dissolution rate of the top TiO 2 nanotubes is equal to the growth rate of the

nanotubes, an equilibrium stage will be entered, and the length of nanotubes will not increase again.

For different electrolyte systems and anodizing processes, the equilibrium phase is also different.

8
Therefore, nanotubes of various lengths are formed [38].

3.2. The Effect of Subsequent Ultrasonic Treatment on Morphology of Samples

After the reaction was completed, the obtained sample was taken out, and the insulating tape on the

back side of the sample was removed (since the back was sealed with insulating tape before the

reaction to ensure the oxidation of one side). Then, the sample was gently sonicated with anhydrous

ethanol and deionized water for 10 minutes in an ultrasonic cleaner, and the ultrasonic power should

not be too strong, which is 30% of the normal power. If the power is too large, the nanotubes are easy

to fall off from the titanium matrix [39]. Fig. 1 (A) and Fig. 1 (B) are SEM images of the same sample

before and after ultrasonic cleaning. In the SEM image of Figure 1 (A), the surface of the nanotubes is

covered with a number of nanotube fragments. As shown in Fig. 1 (B), after ultrasonic cleaning, the

nanotube fragments disappear completely. This shows that ultrasonic cleaning can remove the

nanotube fragments from the surface of the nanotube arrays. In addition, ultrasonic cleaning with

anhydrous ethanol and deionized water respectively, can remove the residual electrolyte components in

the surface layer. The ultrasonic-cleaned sample was soaked in deionized water for a period of time,

and the liquid composition was analyzed. The results show that there is almost no electrolyte remained.

It should be noted that the ultrasonic time should not be too long to avoid reducing the length of the

nanotubes.

3.3. The Effect of Water Content

Fig. 2 are SEM images of samples obtained when the content of NH 4F in EG + NH4F + H2O

electrolyte system is kept at 0.3wt%, the anodizing time is 3h, the oxidation voltage is 40V, and the

water content is 1 vol%, 2 vol%, 3 vol%, and 4 vol% respectively at room temperature. From Figure 2

(A) to Figure 2 (C), the nanotube diameter increased slightly. The reason for the above phenomenon in

9
Figure 2 (A) is as follows: according to the growth mechanism of TiO 2 nanotube arrays, there are two

corrosions in the growth process, including the corrosions of nanotubes by electrolyte itself and by

electric-field-supported electrolyte. Compared with the water-based electrolyte system, as a result of

the viscosity of the organic solvent is much larger than that of water, the diffusion rate of H + generated

at the bottom of the TiO2 nanotube in the organic electrolyte system to the port is greatly reduced. At

the same time, the corrosion ability of the electrolyte itself is also reduced [40]. In this paper, from

Figure 2 (A) to Figure 2 (D), the content of H 2O in the electrolyte gradually increases, resulting in a

gradual decrease in the viscosity of the electrolyte, thus increasing the rate of migration of H+

migration from the bottom of the nanotube to the port. At the same time, the corrosion of the

electrolyte to the nozzle is accelerated. Therefore, from Fig. 2 (A) to Fig. 2 (C), the corrosion ability of

the electrolyte to the nozzle is gradually enhanced, and the nanotube wall is gradually corroded and

thinned, and the diameter of the nanotube is gradually increased. As shown in Fig. 2, some nanotube

nozzles and parts below the nozzle have been completely corroded, or a small number of nanotubes are

stacked one on another. The degree of corrosion of nanotube nozzles from Fig. 2 (C) to Fig.2 (D) is

greatly deepened. The increase of water content leads to the corrosion of most nanotube nozzles, and

the corrosion of the parts below the nozzles is also severe. Therefore, in Fig. 2, some tubes are stacked

on each other and most of the nozzles are completely corroded, only a few nanotubes are intact.

In summary, TiO2 nanotubes with open upper end, closed lower end and independence can be

obtained in EG +0.3 wt% NH4F + H2O electrolyte system. The content of water in the electrolyte has a

certain influence on the morphology of nanotube arrays. With the increase of water content, the

diameter of nanotubes increases slightly. When the water content exceeds 2 vol%, the nozzle of the

nanotube is damaged. With the increase of water content, the corrosion will become more serious, and

10
even the nozzle will be completely corroded. It can be seen that the content of water in the electrolyte

system has an important influence on the preparation of TiO 2 nanotube arrays during anodization

process. When the content of water is 2 vol%, the morphology of TiO2 nanotubes is the best. To

determine the surface chemical composition and the oxidation states of the elements in the TiO2

nanotube arrays under the water content 2 vol%, we have done the XPS measurements (detailed data

can be found in Appendix A-Fig. 1).

3.4. The Effect of Anodizing Time

Figure 3 are the SEM images of the side view and top view of the obtained sample in an EG

+0.3wt% NH4F + H2O electrolyte system at room temperature with a water content of 2 vol%, an

oxidation voltage of 40 V, and an oxidation time of 1 h, 3 h, 5 h, and 7 h respectively. From Fig. 3 (A)

to Fig. 3 (D), the anodizing time increases sequentially, which are 1 h, 3 h, 5 h, and 7 h, respectively. It

can be seen from the figure that TiO2 nanotubes have been formed during this oxidation period. From

the mechanism analysis, it can be seen that TiO2 nanotubes have entered the growth period. The inset

in the upper right corner of the four figures is a front top SEM image of the sample obtained at each

corresponding time and magnified 120,000 times. It is observed that as the anodizing time increases,

the diameter and wall thickness of the nanotubes slightly change. This shows that once the TiO 2

nanotubes are formed, the anodizing time has little effect on the tube diameter and wall thickness of the

nanotubes within a certain period of time. The tube lengths corresponding to the side SEM images of

the samples in Figure 3 (A) to Figure 3 (D) are approximately 5 μm, 10 μm, 15 μm, and 20 μm,

respectively. The high-quality TiO2 nanotube samples up to 20 um in length-higher than the lengths

prepared in most of the current studies[40]. This shows that the anodizing time has a great influence on

the length of the nanotubes in a certain period of time, and with the extension of anodizing time, the

11
length of nanotubes also increases. The reasons for this situation are as follows: according to the

mechanism analysis, the length of TiO2 nanotubes depends on three aspects: the corrosion rate of the

electrolyte on the TiO2 nanotube port under electric field, the corrosion rate of electrolyte on TiO2 at

the bottom of TiO2 nanotubes and the interface of oxide film under electric field, and the formation rate

of TiO2 at the interface between oxide film and substrate. After oxidation is carried out for a period of

time, the speeds of the latter two will be equal. At this time, the barrier thickness of the TiO 2 nanotubes

will no longer change, and the speeds of the two is the growth rate of the TiO 2 nanotubes. In a certain

period of time, the growth rate of TiO2 nanotubes is faster than the corrosion rate of electrolyte to TiO 2

nanotube ports under electric field. Therefore, at this stage, the length of nanotubes increases with the

extension of anodizing time. In addition, studies have shown that the length of TiO 2 nanotubes is not

always increase with the increase of oxidation time [41]. With the prolongation of anodic oxidation

time, the concentration of fluorine ions in the electrolyte decreases continuously, and the mass transfer

speed in the tube also decreases continuously [42]. At this time, the growth rate of the nanotubes

decreases. When the dissolution rate of TiO 2 nanotubes is equal to the growth rate, an equilibrium state

is reached, at which time the length of the nanotubes remains unchanged [43]. To sum up, before the

anodization reaches equilibrium, during the growth phase of TiO2 nanotubes, the anodizing time has no

significant effect on the tube diameter and wall thickness, but has a great effect on the tube length. The

length of nanotubes increases with the increasing of anodizing time. Therefore, in the experiment, we

can further control the length of TiO2 nanotubes by controlling the anodizing time. The optical

reflection curves of the samples are different under different oxidation time (detailed data can be found

in Appendix A-Fig. 2).

Figure 4 is the XRD pattern of the samples obtained at room temperature in EG + 0.3 wt% NH4F +

12
H2O electrolyte system with water content of 2 vol%, oxidation voltage of 40 V and oxidation time of 1

h, 3 h, 5 h and 7 h respectively. In the figure, A represents a characteristic diffraction peak of the TiO 2

anatase phase, and T represents a characteristic diffraction peak of the metal titanium. The

characteristic diffraction peaks at 2θ of 25.4°, 38.7°, 47.9°, 53.8°, and 55.0° in the figure correspond to

the (101), (112), (200), (105), and (211) crystalline plane respectively of anatase phase of titanium. The

characteristic diffraction peaks at 2θ of 38.3°, 40.1°, 53.1°, 63.1°, 70.8°, and 76.3° correspond to (002),

(101), (102), (110), (103) and (112) crystal plane of metallic titanium, respectively. It can be seen from

the figure that during the oxidation process, there is no significant change in the position and intensity

of the diffraction peak with time. The crystal structure of the obtained samples does not change.

Therefore, the change of anodizing time has no effect on the crystal structure of the TiO2 nanotubes.

Figure 5 are the SEM images and the FETEM diagram of TiO 2 nanotube arrays with optimal

morphology prepared in an EG + 0.3 wt% NH4F + H2O electrolyte system at room temperature with

the water content of 2 vol%, the anodizing time of 3 h, and the oxidation voltage of 40 V. As seen from

Fig. 5 (A) and Fig. 5 (B), the obtained samples are the nanotubes with open upper end, closed lower

end. Fig. 5 (C) is a FETEM diagram of a plurality of nanotubes. The tubular structure of the sample is

clearly visible, and there is a gap between the tube and the tube, which is not adhered together but

independence. To study the porosity type and also the pore diameter of the prepared TiO 2 nanotube

arrays with optimal morphology, we have done the Brunauer-Emmett-Teller (BET) test (detailed data

can be found in Appendix A-Fig. 3).

3.5. Effect of Different Water Content on DSSC Performance

The preparation parameters of the TiO2 nanotube arrays used in this section are as follows:

electrolyte system EG + 0.3 wt% NH4F + H2O at room temperature with an anodizing time of 3 h, and

13
an oxidation voltage of 40 V, a water contents of 1 vol%, 2 vol%, 4 vol% respectively. The

morphology of the prepared nanotube arrays correspond to (A), (B), and (D) in Fig. 1. The TiO 2

nanotube arrays prepared under the water contents of 1 vol%, 2 vol%, and 4 vol% respectively were

assembled as photoanodes to form DSSCs. Then their optoelectronic properties were tested. Figure 6

(A) and 6 (B) respectively show the J-V curves and output power curves of DSSCs when TiO2

nanotube arrays prepared under different water content conditions are used as photoanodes. In Fig. 6

(A), a, b, and c correspond to J-V curves of DSSCs prepared by TiO2 nanotube arrays prepared under

the water contents of 4 vol%, 1 vol%, and 2 vol% respectively. The open-circuit photovoltage (Voc) and

short-circuit photocurrent (Jsc) of the DSSC can be directly obtained from the intercept of the abscissa

and the ordinate in the figure 6 (A). The output power curve can be obtained directly from the

photocurrent and photovoltage. The output power curve is obtained by multiplying the values of

abscissa and ordinate coordinates and plotting the product results relative to the photovoltage. Fig. 6 (B)

is output power curves of DSSCs when TiO2 nanotube arrays prepared under three different water

contents are used as photoanodes. Wherein a, b, and c correspond to the output power curves of the

DSSCs prepared by the TiO2 nanotube arrays under the the water contents of 4 vol%, 1 vol%, and 2

vol% respectively. The photocurrent and photovoltage corresponding to Popt are Jopt and Vopt, so the fill

factor (FF) of the battery can be calculated according to the formula (1-5). The photoelectric

conversion efficiency η is the ratio of the maximum output power (Popt) of the battery to the input light

power (Pin). The total photoelectric conversion efficiency can be obtained from formula (1-6), where

the input light power Pin is 100 mW/cm2 [44]. The performance parameters of DSSCs prepared by

samples under different water content conditions are shown in Table 1.

Jopt × Vopt
FE = Jsc × Voc (1-5)

14
 Popt
Jsc × Voc × FE
η= Pin = (1-6)
Pin

It can be seen from figure 6 (A), 6 (B) and Table 1 that the performance of DSSC first increases and

then decreases when the water content in the electrolyte system increases from 1 vol% to 4 vol%.

When the water content increases from 1 vol% to 2 vol%, J sc increases from 2.56 mA/cm2 to 3.02

mA/cm2, FF increases from 0.48 to 0.50, and η increases from 0.75% to 1.07%. When the water

content of 4 vol%, the performance of DSSC is drastically decreased, and its performance is even

lower than that when the water content is 1 vol%, and the photoelectric conversion efficiency even

drops to 0.25%. After analysis, the appearance of this situation and the change of morphology have a

great relationship. According to figure 1, as the water content in the electrolyte system increases, the

diameter of the nanotubes gradually increases. When the water content is 3 vol%, the nanotube orifice

is damaged, and a few nanotubes are piled up. When the water content reaches to 4 vol%, the orifice of

the nanotube shows serious damage, and some nanotubes are piled up. According to the working

principle of DSSC, the TiO 2 nanotube arrays play the role of adsorbing dye and conducting electrons.

The larger the specific surface area of the nanotube is, the more the adsorption of the dye. The increase

in the diameter of the nanotubes increases the specific surface area of the nanotubes. Therefore, when

the water content is 2%, the performance parameters of the prepared DSSC are improved. However,

when the water content is 4%, the adsorption of dye on the nanotubes is greatly reduced due to the

serious damage of the nanotubes, resulting in the decrease of photocurrent. In addition, the stacking of

some nanotubes prevents the transfer of electrons in the electrolyte to a certain extent, which increases

the probability of I/I3- recombination in the conduction band, increases the dark current and leads to the

reduction of open circuit voltage. Therefore, the performance parameter of DSSC decreases sharply.

3.6. Effect of Different Anodizing Time on DSSCs Performance

15
 The preparation parameters of the TiO2 nanotube arrays used in this section are as follows:

electrolyte system EG + 0.3 wt% NH4F + H2O at room temperature with a water content of 2 vol%, an

oxidation voltage of 40 V, and the anodizing time of 1h, 3h, 5h, 7h, respectively. The morphology of

the prepared nanotube arrays is shown in FIG. 2. Figure 7(A) and 7(B) respectively show the J-V

curves and output power curves of DSSCs when TiO2 nanotube arrays prepared under different

anodizing time conditions are used as photoanodes. Therefore, the performance parameters of DSSCs

prepared by samples under different water anodizing time are shown in Table 2. To study the dye

adsorption value, the desorption dyes were determined by UV-vis spectroscopy. The dyes were

desorbed from dye-coated electrodes into 0.1 M KOH for 15 min. Using Beer’s law, the dye loading

can be calculated by fitting the absorption at 510 nm to the calibration curve. The amounts of dye by

the samples at different oxidation times (1 h, 3 h, 5 h and 7 h) are 1.92×10 -8 mol/cm2, 3.95×10-8

mol/cm2, 5.91×10-8 mol/cm2, and 7.52×10-8 mol/cm2, respectively.

It can be seen from the above analysis that the anodizing time has a great influence on the length of

the TiO2 nanotubes. Within a certain time range, the length of TiO 2 nanotubes increases with the

increase of anodizing time. The lengths of the nanotubes under the anodizing time of 1 h, 3 h, 5 h, and

7 h correspond to about 5 μm, 10 μm, 15 μm, and 20 μm respectively. As shown in figure 7 (A) and

Table 2, as the anodizing time increases, J sc gradually increases. This is because with the prolongation

of anodizing time, the tube length of TiO 2 nanotubes increases gradually, and the increase of nanotube

length leads to the increase of specific surface area of nanotubes. Therefore, the number of dye

molecules adsorbed by nanotubes also increases. The increase of the number of adsorbed dye

molecules directly leads to the increase of photogenerated carriers per unit time, thus increasing the

photocurrent.

16
 It can also be concluded from the above data that V oc and FF both increase first and then decrease

with the increase of anodizing time. This is because the length of nanotubes gradually increases with

the anodizing time. When the length of the nanotube increases to a certain extent, the propagation path

of photogenerated electrons in the nanotube becomes longer. Therefore, the recombination probability

of electrons in the conduction band with oxidized dye and I3 - in electrolyte solution is increased, and

the reaction rate constant of dark current is increased. The open circuit voltage is inversely proportional

to the dark reaction rate constant, so the open circuit voltage is reduced. To sum up, with the increase

of oxidation time, the J sc of DSSC increases, while FF and V oc both increase first and then decrease in a

certain period of time. When the anodizing time is 5 h, the FF reaches the maximum of 0.55 and the

Voc reaches the maximum of 0.71. The photoelectric conversion efficiency η increases with the

increase of anodizing time. When the anodizing time is 7 h, η increases to 1.96%.

In recent years, the efficiency of preparing undoped and unmodified TiO 2 nanotubes as photoanodes

for DSSC is shown in Table 3. The main work of our research is to systematically study the effects of

preparation conditions on morphology. And on this basis, the battery efficiency was studied

secondarily. Our battery efficiency is indeed not ideal. In the future work, we will start from several

aspects such as doping, preparation of anti-reflective structure, and increase utilization efficiency of

incident photons to improve battery performance.

4. Conclusions

Through the characterization and analysis of samples prepared under different anodic oxidation

conditions, the effects of water content in electrolyte, anodizing time and ultrasonic post-treatment on

the morphology and crystal structure of TiO2 nanotube arrays were studied. The morphology of

nanotube array prepared in an EG +0.3 wt% NH4F + H2O organic electrolyte system at room

17
temperature with a water content of 2 vol%, an anodizing time of 3 hour, and an oxidation voltage of

40 V is the best. Under the same conditions, before the balance of anodic oxidation is reached, the

oxidation time has no significant effect on the diameter and wall thickness of the TiO2 nanotubes

during the growth phase, but has a great influence on the tube length. The length of the nanotubes

increased with the extension of the anodizing time. Moreover, the anodizing time has no significant

effect on the crystal structure of TiO2 nanotube arrays. During the post-treatment of the sample, gentle

ultrasonic cleaning can remove the residual nanotube debris from the surface, as well as the residual

electrolyte composition. TiO2 nanotube arrays have excellent properties such as the high aspect ratio,

high specific surface area and high efficient electron transport channel. Based on the above properties,

we have studied its application in dye-sensitized solar cells based on dye N-719. By testing the

photoelectric performance of DSSCs when TiO2 nanotube arrays prepared under different anodization

parameters are used as photoanodes, the effects of different anodization parameters on the photovoltaic

performance of DSSC were obtained. Finally, the process parameters that optimize the photoelectric

conversion efficiency of DSSC were obtained. The content of water in EG + 0.3 wt% NH 4F + 2%H2O

of organic electrolyte system has an important influence on the performance of DSSC. With the

increase of water content, DSSC performance first becomes good and then decays. When the water

content is 2 vol%, DSSC performance is the best, in which Jsc = 3.02mA/cm2, Voc = 0.69v, FF = 0.50, η

= 1.03%. Within a certain time range, with the extension of anodizing time, Jsc and η increase

continuously, while Voc and FF increase first and then decrease. The optimal photoelectric performance

obtained is Jsc = 5.2mA/cm2, Voc = 0.7V, FF = 0.54, and η = 1.96%.

Acknowledgements

18
 This research was funded by the National Natural Science Foundation of China (NNSFC), grant

numbers 51606158, 11604311 and 11704223; funded by the Natural Science Foundation of Fujian

Province, grant number 2018J05008 and JZ160459; Funded by Sichuan Science and Technology

Program, grant number 2018GZ0521; Funded by Longshan academic talent research supporting

program of SWUST, grant number 18lzx506; Funded by PhD Research Startup Foundation of

Quanzhou Normal University (G16057); and funded by the Distinguished Young Scholars Program

of Fujian

Province (C18032).

Declarations of interest: none

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in the online version, at…..

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 Table

Water Content Jsc(mA/cm2) Voc(V) Jopt(mA/cm2) Vopt(V) FF η(%)

1vol% 2.56 0.61 1.92 0.39 0.48 0.75

Table 1. Performance comparison of DSSCs when TiO2 nanotube arrays prepared under different
2vol% 3.02 0.69 2.03 0.51 0.50 1.03
water contents are used as photoanodes
4vol% 1.72 0.38 1.27 0.20 0.39 0.25

Anodizing Time(h) Jsc(mA/cm2) Voc(V) Jopt(mA/cm2) Vopt(V) FF η(%)

1 2.02 0.6 1.52 0.33 0.42 0.50

3 3.02 0.69 2.03 0.52 0.49 1.03

5 3.95 0.71 3.08 0.51 0.55 1.54

26
7 5.2 0.70 4.26 0.46 0.54 1.96

Table 2. Performance comparison of DSSCs when TiO2 nanotube arrays prepared under different

anodizing times are used as photoanodes

Variable Electrolyte Composition η(%) Ref.

Water Content EG + 0.2M HF + 1-2M deionized water. Anodization was 0.53-1.59 [45]

performed at 10 V for 24 h.

Anodizing Time EG + 0.5M HF 48%. Anodized at 120 V for 10 min, 1 h, 0.04-1.64 [46]

2 h, and 3.5 h.

Anodizing Voltage EG + 0.4 wt% NH4F + 5 %wt deionized water. Various 0.3-2.0 [47]

anodization voltages from 10 to 50 V were applied for 3

h.

Table 3. Experimental conditions to obtaine efficiency.

27
List of figures

Figure 1. The SEM images of the surface before and after ultrasonic cleaning.

Figure 2. The SEM images of the samples prepared under different water contents, the water content

respectively is: (A): 1 vol%, (B): 2 vol%, (C): 3 vol%, (D): 4 vol%.

Figure 3. The SEM images of the samples prepared under different anodizing times, the anodizing time

respectively is: (A): 1 h, (B): 3 h, (C): 5 h, (D): 7 h. The inset images are the over-view of

corresponding samples.

Figure 4. The XRD patterns of samples prepared under different anodizing times.

Figure 5. The SEM images of the best morphology sample: (A)top view of TiO2 nanotube array, (B)

bottom view of TiO2 nanotube array. (C) The FETEM diagram of the best morphology sample.

Figure 6. (A) J-V curves and (B) output power curves of DSSCs when TiO2 nanotube arrays prepared

under different water contents are used as photoanodes.

Figure 7. (A) J-V curves and (B) output power curves of DSSCs when TiO2 nanotube arrays prepared

under different anodizing times are used as photoanodes.

28
 Figure 1.

Figure 2.

29
Figure 3.

Figure 4.

30
Figure 5.

Figure 6.

Figure 7.

31
 Appendix A. Supplementary data
Synthesis, surface properties, crystal structure and

dye-sensitized solar cell performance of TiO2 nanotube arrays

anodized under different parameters

Zao Yi 1,3, Yu Zeng 1, Hui Wu1, Xifang Chen 1,3, Yunxia Fan1,3, Hua Yang2, Yongjian Tang3, Yougen

Yi4, Junqiao Wang5, and Pinghui Wu6

1 School of Science, Southwest University of Science and Technology, Mianyang 621010, China

2 State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou

University of Technology, Lanzhou 730050, China

 Correspondence should be addressed to Pinghui Wu

Tel: 86-0595-22003815; Fax: 86-0595-22003815

E-mail address: phwu@zju.edu.cn

32
 3 Sichuan Civil-Military Integration Institute, Mianyang 621010, China

4 College of Physics and Electronics, Central South University, Changsha 410083 China

5 School of Physics and Engineering and Key Laboratory of Materials Physics of Ministry of

Education of China, Zhengzhou University, Zhengzhou 450001, China

6 Research Center for Photonic Technology, Key Laboratory of Information Functional Material for

Fujian Higher Education, Quanzhou Normal University, Fujian 362000, China

Fig. 1. XPS survey data of the sample under the water content 2 vol%.

Fig. 1 shows the XPS survey spectra of the sample under the water content 2 vol%. It can be observed

that the TiO2 nanotube arrays contain mainly Ti, O and C elements. The photoelectron peak for Ti2p

appears clearly at a binding energy of 459 eV, O1s at 530 eV and C1s at 284 eV. The XPS peak for

C1s (which served as internal standard) was observed due to the adventitious hydrocarbon from the

XPS instrument itself.

33
 Fig. 2 The Reflection spectra of samples prepared under different anodizing times.

Fig. 2 shows a reflectivity contrast diagram of TiO 2 nanotube arrays under different anodizing

times: 1 h, 3 h, 5 h, 7 h. The reflectivity of the light wavelength range from 200 nm to 900 nm. As can

be inferred from the comparison, with the increase of anodizing times, in different light bands, the

change of reflection efficiency is different. In the short wavelength region (200 nm ~ 400 nm), the

reflection efficiency will not change. However, in the long wavelength region (400 nm ~ 900 nm), the

reflection efficiency increases with the increase of oxidation time. This is because the length of

nanotube arrays increases with the increase of oxidation time, which increases the absorption of visible

light.

Fig. 3 The N2 adsorption desorption BET isotherms of sample prepared TiO2 nanotube arrays with

optimal parameters.
34
The Brunauer-Emmett-Teller (BET) specific surface area (SBET) of the sample was analyzed by

nitrogen adsorption in a Micromeritics ASAP 2020 nitrogen adsorption apparatus (USA). The

as-prepared sample was degassed at 100℃ prior to nitrogen adsorption measurements. Fig. 3 shows the

N2 adsorption-desorption isotherms of the TiO2 sample obtained with optimal parameters. Here, in this

paper, the Ti substrate has been removed. The BET surface area are 29.8 m3/g.

Highlights

> Preparation of TiO2 nanotube arrays by anodic oxidation.

> The optimum parameters of the water content in electrolyte, anodizing time and ultrasonic

post-treatment were determined.

> The effects of each parameter on the morphology and crystal form of TiO2 nanotube arrays was

studied.

>The effects of TiO2 nanotube arrays with different anodization parameter on the photoelectric

performance of DSSC were obtained.

Graphical Abstract

Manuscript title:

Synthesis, surface properties, crystal structure and dye-sensitized solar cell performance of TiO 2

nanotube arrays anodized under different parameters

35
Authors: Zao Yi, Yu Zeng, Hui Wu, Xifang Chen, Yunxia Fan, Hua Yang, Yongjian Tang, Yougen Yi,

Junqiao Wang, and Pinghui Wu

36