聚（N-乙烯基吡咯烷酮）的界面改性以改善反向有机太阳能电池资源-CSDN文库

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Interfacial modiﬁcation for improving inverted

organic solar cells by poly(N-vinylpyrrolidone)

Xuan Yu,†

Xiaoming Yu,†

Jianjun Zhang,

Dekun Zhang,

Hongkun Cai

and Ying Zhao

The eﬀect of the thickness of the poly(N-vinylpyrrolidone) interface

modiﬁer on the photovoltaic performance of inverted organic solar

cells was investigated. Superior interface properties provided eﬃcient

charge transport and decreased the charge recombination due to PVP

interlayer, which reduced the energy barrier for electron extraction by

lowering the hydroxide radical amount. We obtained an enhanced

eﬃciency of 4.55% (for the P3HT:PCBM device) and 6.18% (for the

PTB7:PC

BM device).

Organic photovoltaics (OPVs) based on a conjugated polymer–

fullerene bulk heterojunction (BHJ) are attractive because their

solution processing provides the advantage of low fabrication-

cost and potential in large-scale commercial use.

1–5

Remark-

able progress in the photovoltaic application eld has been

achieved during the last decade; device power conversion

eﬃciency (PCE) has increased from less than 1–8% (for

conventional structure devices) and over 9% (for inverted

structure devices).

6–12

Inverted organic solar cells (IOSCs) in

which an electron transport layer (ETL) is introduced between

the ITO and BHJ layer, with high PCE and better stability in the

atmosphere, are gaining more attention and are under intense

investigation.

10,11,13–17

Due to their eﬃcient electron transport

properties, zinc oxide (ZnO)

15–19

and doped-ZnO (e.g. Ga-doped

ZnO, Al-doped ZnO(AZO))

20–23

have been explored as an ETL in

IOSCs and are compatible with large-area fabrication methods.

However, the surface of ZnO (or AZO) ETLs may cause

incomplete ligand removal and lead to bad control over the

electronic surface properties during the low processing

temperatures,

which leads to inferior interface contact quality

between the inorganic ETL and organic BHJ layer; this imposes

a restriction on further improving the performance of IOSCs as

a result of poor electron extraction

and bimolecular recom-

bination.

To resolve this issue and achieve higher module

eﬃciencies, interface modication becomes a critical factor in

improving the performance of IOSCs.

27,28

An interfacial layer has

been introduced on the ETL to improve the contact quality and

electron extraction. It is suggested that the interfacial layer can

serve multiple functions, including: ① tuning the energy level

alignment, ② improving charge selectivity, ③ controlling

surface properties, ④ introducing optical spacer and plasmonic

eﬀects and ⑤ improving the interfacial stability.

However,

interfacial materials that simultaneously possess these

requirements are rare.

Several classes of interfacial materials have been designed

for improving the interface between the inorganic ETL and

organic BHJ layers in IOSCs such as C

-substituted benzoic

acid,

phosphoric acid-anchored C

self-assembled mono-

layers (SAMs),

conjugated polyelectrolyte,

and cross-linked

fullerenes (C-PCBSD).

More recently, C. Gu et al. demon-

strated that the eﬃ ciency can be further enhanced by inte-

grating optimization of both the anode and cathode interlayer.

In our previous study, poly(N-vinylpyrrolidone) (PVP) was

demonstrated to be a promising candidate interface material

for IOSCs.

It can provide an excellent interface property and is

fully compatible with roll-to-roll production techniques,

because the approach does not need chemical synthesis and

can be easily conducted at room temperature open to air.

Moreover, unlike some SAMs that may cause damage

via

corrosion, the compatibility of PVP interlayer with the upper

and lower layers in the device does not need to be carefully

considered. However, the inuence of PVP thickness on device

performance is not clear. Alex et al. suggested that the thickness

of the inserting layer should be well controlled to tune the

interfacial properties.

Furthermore, non-conformal coverage

of PVP

has a great inuence not only on the properties of

PVP/AZO layers and the surface morphology of the active layer,

but also on the interface characteristics, which should be

changed with PVP thickness. Moreover, the working mecha-

nism between the PVP interlayer and AZO ETL is unclear.

Innovation Application Institute, Zhejiang Ocean University, Zhoushan, Zhejiang,

China, 316022

College of Electronic Information and Optical Engineering, Nankai University,

Tianjin, China, 300071. E-mail: jjzhang@nankai.edu.cn; Fax: +86-22-23508032;

Tel: +86-13820739160

† Xuan Yu and Xiaoming Yu contributed equally to this work.

Cite this: RSC Adv.,2015,5, 58966

Received 20th May 2015

Accepted 25th June 2015

DOI: 10.1039/c5ra09427e

www.rsc.org/advances

58966 | RSC Adv.,2015,5, 58966–58972 This journal is © The Royal Society of Chemistry 2015

RSC Advances

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Therefore, the close relationship between PVP thickness and

photovoltaic performance of IOSCs and PVP working principle

is meaningful for further investigation.

In this manuscript, we present a detailed study on the

correlation between the performance parameters of IOCSs and

changes in the surface morphology, wettability, optical trans-

mittance and WF of the PVP/AZO composite lm as a function

of PVP weight ratio. Results indicate that device performance is

intensely dependent on PVP thickness. With an optimized

thickness, IOSCs based on both poly(3-hexylthiophene)

(P3HT):(6,6)-phenyl C

butyric acid methyl ester (PCBM) and

thieno[3,4-b]thiophene/benzo-dithiophene (PTB7):[6,6]-phenyl

-butyric acid methyl ester (PC

BM)

show a signicant

improvement in PCE, beneting from the lowered contact

barrier and depressed recombination achieved by lowering the

amount of hydroxide radicals present.

The AZO thin lm was prepared from a precursor solution in

which zinc acetate (Zn(CH

)

$2H

O) and aluminum nitrate

(Al(NO

)

$9H

O) were dissolved in ethanol.

The molar

concentration of zinc acetate in the solution was 0.1 M. The

solution was spin-coated on cleaned ITO-substrates at 2000 rpm

for 30 s, which were subsequently thermally treated at 300



C for

30 min in air.

PVP with molecular weight of 30 k from the Tianjin Guang

Fu Fine Chemical Research Institute was dissolved in 10 ml

ethanol at diﬀerent weight ratios (0.1, 0.3, 0.6, and 0.9 wt%).

Aer stirring for 30 min at 50



C in air, the solutions that turned

transparent were spin-coated on top of AZO ETL at a speed of

700 rpm for 30 s to form the PVP interlayer. The thickness of the

resulting PVP lm was about 7, 10, 13, and 17 nm, respectively.

The optical microscopy (OM) images of the PVP thin lms with

diﬀerent weight ratios are shown in Fig. 1.

A solution consisting of P3HT (12 mg ml

1

) and PCBM

(10 mg ml

1

) blend in chlorobenzene (CB) was spin-coated on

either bare AZO or AZO/PVP layer and annealed at 120



C for

10 min in air to form an P3HT:PCBM layer of about 200 nm

thickness. PTB7 : PC

BM mixture with a ratio of 1 : 1.5

(PTB7 concentration of 10 mg ml

1

) was dissolved in CB with 3%

1,8-diiodoctane (DIO). The photoactive layer of PTB7:PC

with a thickness of approximately 120 nm was prepared by spin-

coating at 1000 rpm for 1 min. 5 nm MoO

(HTL) and 100 nm Ag

anodes were thermally evaporated through a shadow mask. The

device active area was about 8 mm

. Reference devices without

PVP layers were fabricated under the same conditions.

The surface morphology of PVP thin lm was rst observed

by OM (Nikon ECLIPSE Ti-u) and the surface root-mean-square

roughness (RMS) was characterized using atomic force

microscopy (AFM) (Seiko SPA-400 SPM UNIT). J–V characteris-

tics of the devices were measured under the illumination of an

AM 1.5G (100 mW cm

2

) solar simulator. The WF of the lms

was carried out using a Kelvin probe (KP020). The PL spectra of

the samples were recorded using a steady-state uorescence

spectrometer (FL3-2-IHR221-NIR-TCSPC). Water contact angles

were measured using a KRUSS (DSA100). Thick lms were made

under each weight ratio of PVP (0.1%, 0.3%, 0.6%, and 0.9%) by

spin-coating ve times. Then, these samples were measured

using a Micro-gure measuring instrument (KOSAKA ET200).

We improved the measurement precision by averaging the

testing values of repeated ten measurements. The trans-

mittance spectra of the samples were obtained using a Cary

spectrophotometer (Cary 5000 UV-VIS).

The J–V characteristics and the dark J–V curves of

P3HT:PCBM devices with diﬀerent PVP interlayers are shown in

Fig. 2(a) and (b). Detailed device performances are summarized

in Table 1. By increasing the PVP weight ratio from 0% to 0.6%,

the device performance was enhanced: the short current density

) increased from 8.05 to 11.32 mA cm

2

, open circuit voltage

) enhanced from 0.58 to 0.64 V, ll factor (FF) increased

from 53.5% to 63.5% and PCE improved signicantly from

2.50% to 4.55%. From Table 1, one can see that the photovoltaic

parameters of IOSCs critically depend on the thickness of PVP

interlayer: the device performance improved with increasing

PVP thickness from 0 to 13 nm, while as the PVP thickness was

increased continuously from 13 to 17 nm, all the parameters

showed a slightly declining trend. It is clear that the improve-

ment in the PCE of device mainly arose from the increased FF

and V

, and the devices with PVP interlayer having a thickness

less than or more than 13 nm (0.6 wt%) show a decreased J

This is because an interlayer that is very thin could not provide

an ohmic contact for eﬃcient electron extraction, while a very

thick layer will lead to an increase in the series resistance (R

An ideal solar cell should have a low R

and high shunt resis-

tance (R

) to exhibit an optimized device performance.

listed in Table 1, the device R

decreased from 16.44 to 6.06 U

, while the R

increased from 219.13 to 293.51 U cm

indicating that contact quality between the AZO ETL and the

active layer is signicantly improved.

The lower leakage currents of PVP devices, as shown in

Fig. 2(b), suggest that the built-in potential (V

) increases,

which may strongly inuence charge transport and extraction,

increasing the device V

The V

of the BHJ solar cell is mainly

related to the diﬀerence between the highest occupied molecular

Fig. 1 OM images of the AZO coated with (a) 0.1 wt%, (b) 0.3 wt%, (c)

0.6 wt% and (d) 0.9 wt% PVP.

Communication RSC Advances

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