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Frontiers of Optoelectronics

Front. Optoelectron.    2016, Vol. 9 Issue (1) : 3-37     DOI: 10.1007/s12200-016-0563-x
REVIEW ARTICLE |
Donor design and modification strategies of metal-free sensitizers for highly-efficient n-type dye-sensitized solar cells
Xiaoyu ZHANG1,2,Michael Grätzel2,Jianli HUA1,*()
1. Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, Shanghai 200237, China
2. Laboratoire de Photoniques et Interfaces, Institut des Sciences et Ingénierie Chimiques, école Polytechnique Fédérale de Lausanne, Lausanne, Switzerland
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Abstract

Dye-sensitized solar cells (DSSCs) cannot be developed without the research on sensitizers. As the key of light harvesting and electron generation, thousands of sensitizers have been designed for the application in DSSC devices. Among them, organic sensitizers have drawn a lot of attention because of the flexible molecular design, easy synthesis and good photovoltaic performance. Recently, new record photovoltaic conversion efficiencies of 11.5% for DSSCs with iodide electrolyte and 14.3% for DSSCs with cobalt electrolyte and co-sensitization have been achieved with organic sensitizers. Here we focus on the donor design and modification of organic sensitizers. Several useful strategies and corresponding typical examples are presented.

Keywords donors      organic sensitizers      dye-sensitized solar cells (DSSCs)     
Corresponding Authors: Jianli HUA   
Just Accepted Date: 31 December 2015   Online First Date: 28 January 2016    Issue Date: 18 March 2016
 Cite this article:   
Xiaoyu ZHANG,Michael Gr?tzel,Jianli HUA. Donor design and modification strategies of metal-free sensitizers for highly-efficient n-type dye-sensitized solar cells[J]. Front. Optoelectron., 2016, 9(1): 3-37.
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http://journal.hep.com.cn/foe/EN/10.1007/s12200-016-0563-x
http://journal.hep.com.cn/foe/EN/Y2016/V9/I1/3
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Fig.1  A simple model for device and working principles of a typical DSSC
Fig.2  Energy level diagram and electron transfer processes in a typical DSSC device (vs. the normal hydrogen electrode, NHE). The insert shows several redox potential examples of redox couples: I-/I3-, iodide/triiodide, Ref. [6]; [Co(dmb)3]3+ /2+, cobalt(II/III) tris(4,4′-dimethyl-2,2′-bipyridine) complexes, [Co(dtb)3]3+ /2+, cobalt(II/III) tris(4,4′-ditert-butyl-2,2′-bipyridine) complexes, [Co(bpy)3]3+ /2+, cobalt (II/III) tris(2,2′-bipyridine) complexes, [Co(phen)3]3+ /2+, cobalt(II/III) tris(1,10-phenanthroline) complexes, Ref. [7]; [Co(Cl-phen)3]3+ /2+, cobalt(II/III) tris(5-chloro-1,10-phenanthroline) complexes, [Co(NO2-phen)3]3+ /2+, cobalt(II/III) tris(5-nitro-1,10-phenanthroline) complexes, Ref. [8]; [Co(bpy-pz)2]3+ /2+, cobalt(II/III) bis[6-(1H-pyrazol-1-yl)-2,2′-bipyridine] complexes, Ref. [9
Fig.3  A model for D-p-A structure and common groups for donor, p-bridge and acceptor part
Fig.4  Scheme 1 Molecular structures of dyes 1-15
Fig.5  Scheme 2 Molecular structures of dyes 16-28
Fig.6  Scheme 3 Molecular structures of dyes 29-38
Fig.7  Scheme 4 Molecular structures of dyes 39-48
Fig.8  Scheme 5 Molecular structures of dyes 49-54
Fig.9  Scheme 6 Molecular structures of dyes 55-64
Fig.10  Scheme 7 Molecular structures of dyes 65-70
Fig.11  Scheme 8 Molecular structures of dyes 71-77
Fig.12  Examples of electron-withdrawing groups used in organic sensitizers for DSSCs
Fig.13  Scheme 9 Molecular structures of dyes 78-89
Fig.14  Scheme 10 Molecular structures of dyes 90-95
Fig.15  Scheme 11 Molecular structures of dyes 96-103
Fig.16  Scheme 12 Molecular structures of dyes 104-112
Fig.17  Scheme 13 Molecular structures of dyes 113-116
Fig.18  Scheme 14 Molecular structures of dyes 117-123
Fig.19  Scheme 15 Molecular structures of dyes 124-130
Fig.20  Scheme 16 Molecular structures of dyes 131-139
dyelmaxa)/nm?a)/(M-1·cm-1)lmaxb)/nmJsc/(mA·cm-2)Voc/VFFPCE/%Ref.
14643270012.330.6420.645.08[30]
24502690011.460.6430.664.93[30]
34973760018.630.6340.637.41[30]
45213400013.70.6060.695.7[31]
54913600015.20.6050.686.3[31]
64223770016.810.740.577.08[32]
74272900015.360.690.505.25[32]
84613130014.280.710.606.12[32]
94612710016.260.660.586.17[32]
104802220011.880.580.543.74[32]
114682250010.890.580.603.75[32]
124382942013.00.660.716.00[33]
134552036915.20.720.727.87[33]
14511279004598.920.6300.794.44[34]
155584280049215.370.6510.757.51[34]
164802500050513.80.6320.696.02[35]
17422293674169.20.6250.794.54[36]
18424138344247.30.6030.743.26[36]
19442137004299.720.7870.715.45[37]
415203004908.830.7360.664.32[43]
474280004229.70.6900.684.55[60]
204581980044011.330.7920.716.38[37]
214792180046511.150.7780.695.99[37]
22410194008.880.7640.5603.80[38]
234252710011.610.7660.5865.21[38]
244402840011.710.7090.5924.92[38]
25460240004769.430.5840.693.78[39]
264503100047510.840.5920.694.41[39]
27449230004807.390.5050.662.48[39]
284912230047111.630.6390.685.08[40]
295232790049118.530.6490.718.49[40]
305042720049015.290.6270.726.84[40]
315235820016.580.7560.7419.29[41]
325225710016.280.7790.7489.49[41]
334923300044416.10.7700.668.18[42]
344952400042314.80.7230.667.06[42]
354652100042715.00.7430.667.36[42]
365004500044815.80.7750.668.08[42]
37447270005098.900.7100.704.41[43]
38411243004838.450.7530.704.44[43]
394363000012.200.7640.777.20[44]
404561600015.330.740.667.43[45]
414632530014.390.700.666.65[46]
424805500013.840.7900.758.2[47]
434807380015.70.6900.748.0[48]
444908500017.610.7100.729.1[48]
455503100051314.010.7040.656.4[49]
465383100048713.370.7140.666.3[49]
475423800048513.250.6960.666.1[49]
485172800046814.900.7380.697.5[49]
494722640047810.750.6550.7004.90[50]
505123010048416.500.7340.6848.28[50]
514987.660.9460.6584.76[52]
5248210.10.8930.6816.15[52]
5349016.50.8330.73710.1[52]
5451311.80.8320.7036.91[52]
554442028916.30.730.708.28[33]
564631261416.80.750.708.71[33]
574827020045612.000.670.604.83[54]
584593720044612.500.710.595.24[54]
594457010044412.960.750.616.00[54]
606106611163211.760.4640.6743.7[55]
616158886765013.350.5190.735.1[56]
62406275004227.750.6890.733.90[57]
63420249004257.890.7310.744.27[57]
64430413004266.860.7520.703.61[57]
654852160044110.3590.7150.7225.35[58]
66468343004546.8660.6870.6783.20[58]
674262900012.210.650.594.68[59]
68413212009.420.690.604.01[59]
69486650004439.80.7500.674.92[61]
704985200046610.20.7540.685.23[60]
714711600011.820.7590.655.84[62]
724742000012.620.7890.636.29[62]
734742000011.410.8040.635.76[62]
74412160004.550.6820.692.14[63]
75412210005.270.7110.722.69[63]
764621300010.760.7930.645.51[63]
774661400012.180.8260.656.55[63]
785182290013.770.6150.7055.97[73]
795452360016.910.6720.7178.15[73]
805363730051416.230.6920.7168.04[74]
815464100052912.320.6990.7276.27[74]
825514300053319.690.7000.73110.08[74]
834951720042813.390.680.746.74[75]
844961920043813.180.780.788.02[75]
855211870050813.600.6850.676.24[80]
865232190052215.650.7760.708.50[80]
87500167004797.100.5700.763.11[85]
884971680048212.110.6710.766.14[85]
895242330051613.560.6910.767.12[85]
905144100011.050.690.685.18[95]
915264600013.400.760.737.43[95]
925933370055813.30.6310.766.4[89]
935382410017.10.6420.6757.4[102]
945495580018.80.7170.6739.1[102]
955404030012.70.7300.7126.6[102]
96556338999.350.5450.6853.49[103]
975802884012.320.5950.7085.19[103]
985842370010.780.6450.7154.97[103]
995513639912.100.6100.7285.37[103]
1004923600042915.40.710.677.3[104]
1015012990043715.50.700.626.7[104]
1024275062348310.180.7330.7695.74[105]
103434607824707.890.7670.7654.63[105]
104423399509.90.7700.6504.94[106]
105428296809.30.7390.6894.73[106]
106426335309.90.7800.6905.33[106]
1074434069014.80.7490.6597.29[106]
1085822800015.40.7300.758.4[107]
1095983300011.50.8070.726.7[107]
1105982400013.30.7160.706.7[107]
1115311200011.00.6720.705.2[107]
11254016003.70.5530.781.7[107]
1134842760047118.260.760.7410.20[108]
1144902300048416.760.760.769.67[108]
1154981990049517.810.760.7510.11[108]
1165332590055318.820.710.729.69[108]
Tab.1  Optical properties of mentioned dyes and their device performance with iodide/triiodide electrolyte
dyelmaxa)/nm?a)/(M-1·cm-1)lmaxb)/nmJsc/(mA·cm-2)Voc/VFFPCE/%Ref.
594457010044410.70.920.686.7[7]
1175261730048714.830.7670.6667.57[119]
1185222140050215.580.7970.7128.84[119]
1195342740050815.7116.250.8820.8900.6930.7379.6010.65[119]
1204986400012.00.8300.727.2[120]
1215008100011.90.9000.717.6[121]
1225315920014.320.9070.688.83[122]
1235436910012.790.8850.697.81[122]
1245425050044114.60.8550.708.8[123]
15.90.9100.7110.3[124]
14.10.8760.789.8[125]
1255484750046816.20.8400.7610.3[125]
1265265770013.40.9010.748.86[126]
1275415260014.10.8110.778.72[127]
1285483552853916.750.8300.7069.81[127]
1295572630054016.080.8020.668.57[127]
1305412550053215.350.7900.647.74[128]
1315875570015.60.7430.788.97[129]
1325965710015.20.7160.768.23[129]
1336006240017.60.7450.759.81[129]
1346026900017.90.7610.7410.1[129]
13551250715.810.8970.74410.6[130]
13617.030.9560.77012.5[130]
1374984320015.571.0360.77512.49[131]
15.991.0340.77412.81[131]
18.271.0140.77114.3[4]
Tab.2  Optical properties of mentioned dyes and their device performance with cobalt electrolyte
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