High-Efficiency and High-Color-Rendering-Index Semitransparent

Jan 30, 2018 - As a result, ST-PSCs based on a hybrid PTB7-Th:PC71BM active layer contribute an efficiency as high as 7.13 ± 0.15% and an average vis...
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High-Efficiency and High-Color-Rendering-Index Semitransparent Polymer Solar Cells Induced by Photonic Crystals and Surface Plasmon Resonance Ping Shen, Guoxin Wang, Bonan Kang, Wenbin Guo, and Liang Shen ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b18765 • Publication Date (Web): 30 Jan 2018 Downloaded from http://pubs.acs.org on January 31, 2018

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High-Efficiency and High-Color-Rendering-Index Semitransparent Polymer Solar Cells Induced by Photonic Crystals and Surface Plasmon Resonance Ping Shen, Guoxin Wang, Bonan Kang*, Wenbin Guo, Liang Shen* State Key Laboratory of Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, 2699 Qianjin Street, Changchun 130012, People’s Republic of China.

Abstract: Semitransparent polymer solar cells (ST-PSCs) show attractive potential in such as power-generating windows or building integrated photovoltaics. However, the development of ST-PSCs is lagging behind opaque PSCs due to the contradiction between device efficiency and transmission. Herein, Ag/Au alloy nanoparticles and photonic crystals (PCs) were simultaneously introduced into ST-PSCs, acting compatibly as localized surface plasmon resonances (LSPRs) and distributed Bragg reflector (DBR) to enhance light absorption and transmission. As a result, ST-PSCs based on hybrid PTB7-Th : PC71BM active layer contribute an efficiency as high as 7.13 ± 0.15 % and an average visible transmission beyond 20 %, which are superior to most of already reported results. Furthermore, PCs can partly compensate valley range of transmission by balance reflection and transmission region, yielding a high color rendering index (CRI) of 95. We believe the idea of two light management methods compatibly enhancing performance of ST-PSCs can offer a promising path to develop photovoltaic applications. Keywords: semitransparent polymer solar cells, photonic crystals, localized surface plasmon resonances, distributed Bragg reflector, color rendering index. *Corresponding Author 1

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E-mail: [email protected](L. Shen); [email protected] (B. Kang)

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Introduction: Polymer solar cells (PSCs) possess unique advantages of excellent mechanical flexibility and low-temperature solution processing, which have attracted great attention and investigated systematically by researchers.1-5 The relatively thin active layer6-8 and transparent electrode whatever bottom and top, are the two key elements in semitransparent polymer solar cells (STPSCs). Recently, the power conversion efficiency (PCE) of single-junction PSCs have been reported as high as 12% with novel bandgap polymer materials and optimized device structures,9 and the PCE of ST-PSCs with nonfullerene acceptor have reached 9.77%.10 So far, although remarkable progress has been made in developing efficient ST-PSCs, the PCE of the most devices still lags far behind that of the state-of-art opaque ones.11-15 It is expected that efficiency, transparency and color characterization of ST-PSCs can be further improved by incorporating novel materials for active layers, transparent electrodes and suitable device structure, which possess a tremendous application advantages in such as building integrated photovoltaics (BIPV) and urban esthetics installation.16-22 In practical application, one unique character of ST-PSCs is average visible transmittance (AVT) in the range of visible light, which usually demand above 25% or higher by spectrophotometer for aesthetic and practical window.23-25 For achieving that, different transparent electrodes such as thin film Ag or Au, 26, 27 Ag nanowires,28-30 carbon nanotubes31,32 and graphene33,34 are applied on the PSCs. Betancur et al. reported a non-periodic one dimensional structure of five layers to return the light harvesting capacity of ST-PSCs with a luminosity close to 30%.35 In addition, color is another feature for ST-PSCs, which can be integrated on building windows and jalousie. In 2010, Ameri et al. first reported inverted semitransparent PSCs of the optical perception with CIE 1931.36 The CIE 1931 is the 3

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International Commission on Illumination (CIE) 1931 chromaticity diagram, which can express transparency color perceptions of ST-PSCs by color coordinates (x, y). The criterion is that the color coordinates ST-PSCs are more close to that of its radiant light source, the color neutrality is better.37 Another indicator of neutral color degree is color rendering index (CRI), which can be calculated from transmittance spectra. According to the criterion,38 if the color coordinates approach to the Planckian locus, the chromaticity difference (DC) become lower than 0.0054 and the CRI is considered accurately. Recently, many approaches including extended absorption materials,39,40 new electron transport layer (ETL) with ultrathin Ag electrode,41 and tandem structure42 have been reported to improve CRI of ST-PSCs. Chen et.al. reported ST-PSCs with 6% PCE, 25% AVT and perfect CRI by using the active layer of PBDTTT-C-T:PC71BM.23 In addition, the high-reflection distributed Bragg reflector (DBR) as an effective auxiliary plant can enable almost completely absorption in photonic bandgap region, resulting kinds of colorful STPSCs.43,44 Apart form the color and transmittance characters, high efficiency is also essential for STPSCs, which is always lower than the opaque one.45,46 As transmission depending on the thickness of the active layer and transparent electrodes, it is important to improve the efficiency of ST-PSCs without increasing the total thickness of the device. The light management method of plasmonic effects contains nanoscale metal particles just meet above requirement and can enhance optical absorption effectively through the method of plasmon decay, scattering effect, near-field enhancement.47 Due to the color and chemically stable peculiarity, Ag and Au nanoparticles (NPs) are always selected to trigger near-field enhancement effect by localized surface plasmon resonances (LSPRs).48 When the LSPRs are excited by the incident electromagnetic field, the conduction electrons can improve electromagnetic field around the 4

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induced NPs by collective oscillations.49,50 As LSPRs can be adjusted easily by the shape and size of NPs, tremendous works have been reported that Ag or Au or Ag/Au alloy NPs are arranged in the hole transport layers (HTL),51,52, active layer53-55 or ETL.56 However, most of metal NPs have not been introduced to enhance absorption of ST-PSCs. Herein, an approach was proposed to systematically enhance efficiency and CRI of ST-PSCs, enabled by LSPRs and photonic crystals (PCs). The Au and Ag nanoparticles induced LSPRs dramatically improved incident photo conversion efficiency (IPCE), and the PCs simultaneously enhanced and flatted the transmission spectrum. Ultimately, ST-PSCs with an efficiency of 7.07 ± 0.16 % and CRI of 95 with lower DC of about 0.0025 were obtained. We believe the approach with multiple light management methods can pave the way of application of ST-PSCs. Experiment Section The investigative ST-PSCs have an inverted structure of ITO/poly[(9,9-bis(3′-(N,Ndimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9–dioctylfluorene)](PFN)/ poly[4,8-bis(5(2-ethy lhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b’]dithiopheneco-3-fluorothieno[3,4-b]thiophene-2-carbox ylate] : phenyl-C71-butyric acid methyl ester (PTB7-Th : PC71BM)/MoO3/metal NPs/ MoO3/Ag/[WO3/LiF]2. The pre-printed ITO with a sheet resistance of ~15Ω sq.-1 and transmittance of 86% were pre-cleaned successively by acetone, isopropyl alcohol, soap and deionized water, and dried by N2. Then 3 nm PFN film was spin coated on cleaned ITO without thermal annealing. The blend solution was prepared by dissolving a 1:1.5 weight ratio of PTB7Th (1 Materials, used as received) and PC71BM (1 Materials, used as received) in a mixed solvent of 1, 2-dichlorobenzene (DCB) with 3 vol % of 1,8-diiodoctane (97:3% by volume) additive, which total concentration was controlled at 20 mg ml-1. And then it was spin coated on 5

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PFN film at 2000 rpm for 60 s in a glove box. Then the devices were fabricated by evaporating MoO3 layer (~5 nm) sandwiched different monitor thickness Ag/Au NPs, MoO3 (~5 nm) and top Ag electrode (~15 nm) under a high vacuum (~ 10–5 Pa). Herein, device with different monitor thickness of deposition Ag/Au NPs were named as device A (0 nm/0 nm), B (1.5 nm/0 nm), C (1.5 nm/1 nm), D (1.5 nm/2 nm), E (1.5 nm/3 nm). For well designed devices, cyclical photonic crystal of [WO3(52.3 nm)/LiF(82.5 nm)]2 (λ= 435 nm, named device F), [WO3(61.3 nm)/LiF(96.7 nm)]2 (λ= 510 nm, named device G) and [WO3(69.1 nm)/LiF(109.0 nm)]2 (λ= 575 nm, named device H) were evaporated on the device C under the same vacuum on the top Ag electrode, which shape were determined by cover module. The active area of devices was about 6.4 mm2. For current density (J)-Voltage (V) curves characteristic, air mass 1.5 G simulated irradiation with an Oriel 300W solar simulator with the intensity of 100 mWcm-2 was employed with a computer-programmed Keithley 2601 source meter. The IPCE spectra were obtained with Pharos Technology QEM1000. The transmittance and absorption results for cells were performed by ultraviolet/visible spectrometer (UV-3600, Shimadzu). The thickness of each layer was measured by using spectroscopic ellipsometer (XLS-100, J. A. Woollam) and step profiler (ET 150, KOSAKA). Experimental Results and Discussions The schematic of ST-PSCs and a scanning electron microscope (SEM) image of the MoO3 / Ag(1.5 nm)/Au(1 nm) NPs are shown in Figure 1a and 1b, respectively. Herein, representative materials of PTB7-Th: PC71BM are selected as active layer. As Ag NPs reveal a high electric field enhancement and Au NPs exhibit chemically stable peculiarity, these noble metal NPs are selected and inserted into hole transport layer of MoO3. From Figure 1b, the bigger globular bright spots of Ag NPs with the grain diameters of about 17 nm and the smaller one of Au NPs 6

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with the grain diameters of about 8 nm are random and discrete on the MoO3 films, which can be attributed to the surface energy difference.51,52,57 As the plasmonic effect is tightly related to the size of the particles, we further check the relationship between the monitor thickness of vapor deposition (MTVD) and the statistical average diameter (SAD) of Ag and Au NPs in Figure 1c. The detail parameters are listed in Table1. For achieving better transmittance and neutral color, the modulated PCs covered on the ST-PSCs. To seek the optimal efficiency for ST-PSCs, different grain diameters of Ag and Au NPs are introduced for near-field enhancement of LSPRs. As shown in Figure 2a, the current density (J)voltage (V) curves under 100 mW cm-2 simulated AM 1.5G in ambient air of devices A-E, and more detail parameters are listed in Table 1. The device A as a control ST-PSCs exhibits a relatively low PCE of 5.50 ± 0.15 % with a short circuit current density (Jsc) of 10.38 ± 0.12 mA cm-2 , an open-circuit voltage (Voc) of 0.78 ± 0.01 V, and a fill factor (FF) of 67.9 ± 0.2 %. The device B with 17 ± 1.2 nm Ag NPs exhibits an improved PCE of 6.52 ± 0.14 % with a higher Jsc of 12.04 ± 0.08 mA cm-2. Surprisingly, when 17 ± 1.2 nm Ag and 8 ± 0.5 nm Au NPs were simultaneously inserted, the device C owns optimal PCE of 7.15 ± 0.17 % and Jsc of 13.11 ± 0.11 mA cm-2. It is notable that all devices exhibit the similar Voc about 0.79 ± 0.01 V and the similar fill factor around 68.5 ± 0.2 %, which implies that the built-in potential have not been exchanged by introducing noble metal NPs. The J-V results reveal that the devices efficiency are sensitive to varieties and grain diameters of NPs by LSPRs effect. To further explore improvement Jsc of ST-PSCs with Au/Ag alloy NPs, the IPCE spectra are recorded and drawn in Figure 2b. When 17 ± 1.2 nm Ag NPs introduced, the IPCE spectrum was significantly improved from 325 to 750 nm. The IPCE appears a broad enhancement in the whole absorption range, which can be attributed to an integrated result including localized 7

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surface plasmon resonances effect, back scattering and reflection.58,59 Encouragingly, the device C shows the top IPCE value about 60 % and enhances over all visible region. The changing trend of IPCE spectra agree well with J-V characters and provide a direct evidence that suitable Ag/Au alloy nanostructures play an important role in enhancing absorption of active layer of solar cells. For ST-PSCs, the transmission in visible spectrum is another important parameter. Figure 3a shows the transmittance curves of designed device A-C, and the corresponding AVT values in visible region (380-780 nm) are also listed in Table 2. The transmittance spectra of device A-C are mainly determined by the light-absorbing materials of PTB7-Th : PC71BM and metal NPs. As Ag(17 ± 1.2 nm) NPs are inserted, the transmittance spectra of the device B reduces prominently from 380-780 nm and the AVT drops from 21.90% to 16.80% in comparison with control device A. Likewise, device C with Ag(17 ± 1.2 nm)/Au(8 ± 0.5 nm) alloy NPs shows the lowest transmittance of all visible region and gets the AVT of only 13.56 %. We can infer that in addition to the little intrinsic absorption of metal NPs, the expected improvement of Jsc can be attributed to the utilization of more light by active layer with LSPRs, which is consistent with JV and IPCE spectra. In order to further comprehend the Jsc improvement of device with Au / Ag alloy NPs, the impedance spectroscopy was measured in darkness by Nyquist diagram in a frequency range of 20 Hz to 1 MHz with an alternating current signal of 1 V. As Figure 3b shown, the shapes of semicircles are beneficial to study the interface resistance of ST-PSCs. We found that the control device A own the biggest diameter of the semicircles. However, the diameter of device B decreases efficaciously and the Device C exhibits the smallest one. The results reveal that the optimal device C with Ag(17 ± 1.2 nm)/Au(8 ± 0.5 nm) alloy NPs not only achieves a higher

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absorption via LSPRs but also can effectually decrease contact resistance and enhance hole transporting ability of MoO3 layer, which is consistent with the enhanced photocurrent. Although Ag/Au alloy NPs can improve device efficiency, the simultaneously declined transmittance cannot meet the application requirement of ST-PSCs. In order to satisfy the demand of integrated building windows, photonic crystals (PCs) are also introduced to adjust and improve transmittance spectra. For PCs unit, the high refractive index oxide of WO3 and low refractive index fluoride of LiF are evaporated alternately and meet the formula of

nWO 3 dWO 3 = nLiF d LiF =

λ0 4

, which λ 0 is the center wavelength of reflected region. It is well known

that the more pairs of number of periodic PCs can contribute the lower transmittance and higher reflectance in photonics band gap. In order to flat the transmission spectrum of ST-PSCs, the three center wavelengths were chosen to find which one can effectively enhance CRI. Hence, two pairs of PCs are used and selected 435 nm, 510 nm, and 575 nm as center wavelength. The corresponding ST-PSCs were named as device F-H, respectively. As shown in Figure 4, transmittance of device F-H are all improved above 500 nm compared with device C. Especially, at the range of 380-420 nm and 470-780 nm are both enhanced and flatten for device H, which contributes to improve AVT from 13.56 % to 20.38 %. Since the cycle of the PCs is only two, the reflectance at the center wavelength λ 0 is partly improved, but the photonic bandgap have not formed. The wavelength ranges of λ 0 of device F-G do not fluctuate obviously, but transmittance of long-wavelength light was improved efficaciously. The phenomenon is an integrated result, including the reflectance of PCs, the LSPRs of Ag/Au NPs and scattering effect of Ag/Au NPs with incident sunlight and reflected light of PCs. The detail AVTs of other devices are also listed in Table 2. It confirms that two pairs of PCs have a positive effect on 9

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improving light transmission and flatting the transmittance spectrum, which is helpful to improve CRI. In order to check the electrical properties of ST-PSCs combined Au/Ag alloy NPs and PSc, the IPCE spectra of devices C, F-H were measured and shown in Figure 5a. It can be observed that device G and H improve the IPCE from the range of 390-490 nm and decline above 500 nm compared to that of device C, and the integral current density (ICD) drops to 13.01 and 12.90 mA cm-2, respectively. For device F, the IPCE curve drop obviously above 450 nm, and finally obtain the ICD of 12.87 mA cm-2. It is notable that the variation trends of IPCE match well with the transmittance spectrum of Figure 4. The corresponding J-V curves are plotted in Figure 5b. The variations of Jsc are in accordance with IPCE spectra and the results are shown in Table 1. The excellent device G obtain the Voc of 0.79 ± 0.01 V, Jsc of 13.06 ± 0.07 mA cm-2, FF of 69.1 ± 0.2 %, PCE of 7.13 % ± 0.15 %. To intuitively evaluate the natural lighting character of ST-PSCs, the CRI is calculated through the transmittance spectra, which is determined by the distance between device color coordinates and the Planckian locus, as well as correlated color temperature (CCT), and chromaticity difference (DC). Firstly, we compute the color coordinates (x, y) of CIE 1931 by illuminating the SP-PSCs with AM 1.5G illumination light source, and mark the position on CIE 1931 color space (Figure 6a). From detail map of Figure 6c, it is observed that the color coordinates (0.331, 0.342) of AM 1.5G light source is close to the Planckian locus (black body locus)60,61 and device A, F, G are far away from Planckian locus. The device C has long distance from AM 1.5G light source of (0.331, 0.342), which means that the color perception of AM 1.5G illumination light source change a lot after penetrating through the device C. Gratifyingly, the color coordinates (0.336, 0.349) of device H is the nearest one to that of AM 1.5G and Planckian 10

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locus. The photograph of device H is shown in Figure 6b, which can see the colorful fish and coral clearly through ST-PSCs. As the same distance on CIE 1931 color space from Planckian locus does not represent the same color change, we use the CIE 1960 uniform color space to stamp the color coordinates (u, v) of different devices with AM 1.5G illumination light source (Figure 6d). The color coordinates (0.206, 0.322) of device H is also close to that of AM 1.5G (0.206, 0.318) and Planckian locus. Even the color coordinates in CIE 1960 are resemble to that in Figure 6c, the contrast of devices color coordinates and Planckian locus are more preciseness and intuition. If the color of an illuminant is closest to the color emitted by the black body of the Planckian locus, then the temperature of the black body is the correlated color temperature (CCT) of the illuminant.62 CCT is an important parameter for ST-PSCs in the counting process of CRI, which can obtain from the color coordinates of CIE 1960 and Planckian locus. When the light source of AM1.5G passes through the devices, the CCT have some changes. In Figure 7a, the CCT of 5340K for device H is near to illumination light source of 5575 K, which means the transmitted light greatly retains the natural light characteristics of the radiation source. Figure 7b give the CRI and chromaticity difference (DC) of ST-PSCs. DC is the shortest distance between the color coordinates on the CIE 1960 uniform color space and the black body locus, and can be calculated by the formula of DC = u − u + v − v /

(1)

where (uk, vk) and (ur, vr) are the color coordinates of devices and black body locus that own the same CCT, respectively. If the DC is less than 0.0054, the calculated CRI of ST-PSCs are considered meaningful. For the device A and F under AM 1.5G illumination, the DC are much 11

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higher than 0.0054, hence the corresponding CRI are unbelievable. Even device C owns the highest CRI of 95 with a DC of 0.0044, the CCT is about 8393 K, which is much higher than that of the AM 1.5G illumination light source. The lowest DC of 0.0025 and outstanding CRI of 95 integrate on device H. The standard illuminants D65 is also used to examine the color perception of the ST-PSCs. The CCT, CRI and DC with D65 optical source are illustrated in Fig. 7c and 7d. And the detailed color character parameters of different devices with AM 1.5G and D65 light source are listed in Table 2. Device H shows the brilliant CRI of 95 with the lower DC of 0.0045. And the CCT of device H is 6156 K, which is close to the calculated D65 light source of 6500K. As mentioned in the previous article, device H also shows fine electrical characteristics and excellent transmittance.

Conclusion: In summary, the Au/Ag alloy NPs are successfully introduced to decrease the resistance and enhance the efficiency of ST-PSCs via LSPRs effect. The PCE improved dramatically from 5.50 ± 0.15 % to 7.15 ± 0.17 % with 17 ± 1.2 nm Ag and 8 ± 0.5 nm Au NPs. Then two pairs of PCs covered on the device with optimized Au/Ag alloy NPs can effectively flat and improve the transmittance spectra. By adjusting the center wavelength of PCs, we obtained excellent optical property device with CRI of 95, DC of 0.0025, CCT of 5340 K, AVT of 20.38 % and the electrical characteristics of PCE as high as 7.07 ± 0.16 %. It suggests the method of combining ST-PSCs with multiple light management methods will give a guideline for future commercial application of integrated building windows.

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Acknowledgement: The authors are grateful to National Natural Science Foundation of China (61370046), International Cooperation and Exchange Project of Jilin Province (20170414002GH) for the support to the work. References:

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Figures:

Figure 1. (a) Device architecture of Ag/Au alloy NPs induced ST-PSCs with PCs. (b) SEM image with 140000 times magnification of the MoO3/Ag(1.5 nm)/Au(1 nm). (c) The relationship between the monitor thickness of vapor deposition and the statistical grain diameter of Ag and Au NPs.

Figure 2. (a) J–V characteristics under 100 mW cm-2 simulated AM 1.5G in ambient air and (b) IPCE characteristics of control device A and device B-E with different thickness Ag/Au alloy

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NPs.

Figure 3. (a) Transmittance spectra of devices A-C. The AVT of devices are calculated from 380 to 780 nm. (b) Complex impedance spectra of devices A-C.

Figure 4. Transmittance spectra of device C and devices F-H integrate Ag/Au alloy NPs and PCs with 435 nm, 510 nm and 575 nm. The AVT of devices are calculated from 380 to 780 nm.

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Figure 5. (a) IPCE and (b) J-V characteristics of device C, F-H under 100 mW cm-2 simulated AM 1.5G in ambient air. The inserted photograph is device C, F-H with different color.

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Figure 6. (a) The color coordinates of the ST-PSC devices of A, C, F-H under AM 1.5G illumination light source on the CIE 1931 color space. (b) The photograph of device H. (c) The detailed section of CIE 1931 color space and (d) of CIE 1960 uniform color space under AM 1.5G illumination light source.

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Figure 7. (a) The CCT of different ST-PSCs and (b) the CRI and DC of different ST-PSCs under illumination of AM 1.5G light source. The green dotted line marks the CCT of AM 1.5G illumination light source, and the gray dotted line is the referential DC of 0.0054. (c) The CCT of different ST-PSCs and (b) the CRI and DC of different ST-PSCs under illumination of D65 light source. The blue dotted line marks the CCT of D65 illumination light source, and the gray dotted line is the referential DC of 0.0054.

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Table 1 Photovoltaic parameters for devices with different structure under 100 mW cm-2 simulated AM 1.5G in Ambient Air.

Devices

A

MTVD

SAD

Ag/Au

Ag/Au

(nm/nm)

(nm/nm) 0/

0/0

PCs

w/o PCs

0 B

1.5/0

17±1.2/

w/o PCs

0 C

1.5/1

17±1.2/

w/o PCs

8±0.5 D

1.5/2

17±1.2/

w/o PCs

15±0.6 E

1.5/3

17±1.2/

w/o PCs

26±0.9 F

1.5/1

17±1.2/

λ 0 =435 nm

8±0.5 G

1.5/1

17±1.2/

λ 0 =510 nm

8±0.5 H

1.5/1

17±1.2/

λ 0 =575 nm

8±0.5

Voc (V)

FF (%)

PCE (%)

10.38

0.78

67.9

5.50

±0.12

±0.01

±0.2

±0.15

12.04

0.79

68.5

6.52

±0.08

±0.01

±0.2

±0.14

13.11

0.79

69.0

7.15

±0.11

±0.01

±0.2

±0.17

12.49

0.79

68.7

6.78

±0.08

±0.01

±0.2

±0.15

10.56

0.78

68.4

5.63

±0.07

±0.01

±0.2

±0.12

12.92

0.79

69.0

7.04

±0.12

±0.01

±0.2

±0.17

13.06

0.79

69.1

7.13

±0.07

±0.01

±0.2

±0.15

12.97

0.79

69.0

7.07

±0.09

±0.01

±0.2

±0.16

Jsc (mA cm-2)

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Table 2 The color character parameters of different designed ST-PSCs with AM 1.5G and D65 light source. Devices

A

C

F

G

H

AVT(%)

Light Source

CCT(K)

DC

CRI

AM 1.5G

6990

0.0108

91

D65

8243

0.0129

89

AM 1.5G

8393

0.0044

95

D65

10541

0.0066

94

AM 1.5G

5728

0.0146

87

D65

6480

0.0167

86

AM 1.5G

4550

0.0052

94

D65

5115

0.0072

93

AM 1.5G

5340

0.0025

95

D65

6156

0.0045

95

21.90

13.56

17.52

18.08

20.38

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Table Of Contents (TOC) graphic.

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