New Class of Organic Hole-Transporting Materials Based on

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New Class of Organic Hole Transporting Materials Based on Xanthene Derivatives for Organic Electronic Applications Jefferson Silva Martins, Aloisio Andrade Bartolomeu, Willian Henrique dos Santos, Luiz Carlos da Silva Filho, Eliezer Fernando de Oliveira, Francisco Carlos Lavarda, Alexandre Cuin, Cristiano Legnani, Indhira Oliveira Maciel, Benjamin Fragneaud, and Welber Gianini Quirino J. Phys. Chem. C, Just Accepted Manuscript • Publication Date (Web): 22 May 2017 Downloaded from http://pubs.acs.org on May 23, 2017

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The Journal of Physical Chemistry

New Class of Organic Hole Transporting Materials Based on Xanthene Derivatives for Organic Electronic Applications Jefferson S. Martins†₸*, Aloisio A. Bartolomeu‡, Willian Henrique dos Santos‡, Luiz Carlos da Silva Filho‡, Eliézer Fernando de Oliveira||, Francisco Carlos Lavarda||, Alexandre Cuin₸ᶴ, Cristiano Legnani†₸, Indhira O. Maciel†₸, Benjamin Fragneaud†₸, Welber G. Quirino†₸* †

Laboratório de Eletrônica Orgânica, Departamento de Física, Universidade Federal de Juiz de Fora, 36036-900 Juiz de Fora, MG, Brazil.

₸

Centro de Estudos em Materiais, Instituto de Ciências Exatas, Universidade Federal de Juiz de Fora, UFJF, 36036-900 Juiz de Fora, MG, Brazil.

‡

Universidade Estadual de São Paulo (UNESP), Departamento de Química, 17033-360, Bauru, São Paulo, Brazil.

||

Universidade Estadual de São Paulo (UNESP), Departamento de Física, 17033-360, Bauru, São Paulo, Brazil. ᶴ

Laboratório de Pesquisa em Química Bioinorgânica, Departamento de Química, Universidade Federal de Juiz de Fora, UFJF, 36036-900 Juiz de Fora, MG, Brazil.

1 ACS Paragon Plus Environment


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ABSTRACT: In this work, we investigate the influence of three novels 14-aril-14Hdibenzo[a,j]xanthene derivatives (XDs) modified with different functional groups as very promising hole transporting materials for organic optoelectronic devices. Optical, electronic and structural properties were analyzed by UV-Visible absorption spectrum, cyclic voltammetry and powder X-ray powder diffraction (XRPD). We have investigated the influence of these XD as hole transporting layers (HTL) on the performance of a simple stack bilayer OLED built with commercial aluminum tris (8-hydroxyquinoline) Alq3 acting as an electron-transporting and emissive layer (EML). As a proof-of-principle the XD devices were compared to reference devices fabricated with one of the most common hole transporting materials, the N,N'-bis(naphthalen-1yl)-N,N'-bis(phenyl)-2,2'-dimethylbenzidine (α-NPD). The structure of the devices was ITO/HTL (50 nm)/ Alq3 (50 nm)/Al (120 nm) without encapsulation. Under the same conditions, the devices using XD as HTL exhibited high performance and significant durability when compared to the reference ones. These results are also supported by a theoretical study using Density Functional Theory (DFT) showing that this set of XD presents a higher hole mobility than α-NPD. Thus, we have demonstrated that this class of molecules are very promising when used as hole-transport material in organic electronic devices. 1. INTRODUCTION Since the pioneering work of Tang and Van Slyke1 confirming that the development of highperformance OLEDs is dependent on the high efficiency of charge injection and adequate mobility, various molecules and conjugated polymers have been developed for charge-transporting hosts.2– 8

In the last decades several hole transporting materials (HTM) were developed and mostly consist

of triaryl amines and benzidines in many forms, for instance: i) amine family (TcTa, TPT1),9–11 ii) benzidine family (α-NPD, NPB, TPD),12–14 iii) spiro-linked or spirocyclic fluorine (Spiro-TPD, 2 ACS Paragon Plus Environment

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Spiro-2NPB, Spiro-TAD).15–17 Even though several hole transporting materials with better hole mobility than NPB derivatives have been reported in recent years, the NPB are still considered the most successful HTM and are still largely used in organic devices. Organic electronic is still seen as a growing area since the research and development of novel electronic devices has been pushed toward all-plastic optoelectronic applications. Organic Electronics also includes printed devices, flexible electronics, transparent substrates, vibrating screens that make it pump out sound and all kind of smart devices, making this technology even more innovative, accessible and sustainable. Therefore, the continuous designing of novel and efficient materials with spectral, thermal and morphological stability is a need to overtake this demand. In this context, xanthene derivatives (XD) have generated considerable interest as hole injectors, or transporting injected holes for organic devices (OLEDs, OPVs, and transistors)18–22 due to its low cost, simple synthetic methodology, easy chemical modification, and good thermo-molecular stability.23 Moreover, XD can also employed as blue-emitting materials due to their high photoluminescence (PL) efficiency and wide band gap.24–27 In this work we investigated a novel class of 14-aril-14H-dibenzo[a,j]xanthene complex derivatives modified with different functional groups. It results that these molecules are very promising HTMs for organic devices since they exhibit excellent carrier injection/hole transporting characteristics as well as a good thermo-molecular stability. Conventional bilayer devices using XD as an HTL were fabricated and compared to the reference device fabricated with N,N'bis(naphthalen-1-yl)-N,N'-bis(phenyl)-2,2'-dimethylbenzidine (α-NPD). Electroluminescence, density-voltage (J–V) and luminance–voltage (L–V) characteristics of the devices were obtained



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in detail and showed enhanced optoelectrical performances. On the other hand, we demonstrate that this set of XD present a higher hole mobility than α-NPD by comparing thermal, electrochemical, optical, structural characteristics to a Density Functional Theory (DFT) study. 2. EXPERIMENTAL SECTION 2.1. General Procedure for One-Pot Synthesis of 14-aryl-14h-dibenzo[a,j]xanthene derivatives (XD-01, XD-02 AND XD-03) From a solution of NbCl5 (25 mole %) in anhydrous CH2Cl2 (2.0 mL), maintained at ambient temperature under N2 atmosphere, we added a solution of 2-naphthol (1.0 mmol) and the respective aldehyde (0.5 mmol) in anhydrous CH2Cl2 (4.0 mL). Once the addition was completed, magnetic stirring was maintained at the same temperature for 24 or 48 h. The reaction mixture was quenched with H2O addition (3.0 mL) and the product was extracted with CH2Cl2 (10.0 mL). The organic layer was separated and washed with saturated aqueous NaHCO3 (3 × 10.0 mL), brine (2 × 10.0 mL), dried over anhydrous MgSO4, filtered and the residual solvent evaporated under vacuum. The

residue

was

recrystallized

in

ethanol

to

ensure

high

purity

products

(

Scheme 1). The full experimental details and spectroscopic characterizations (1H and 13C NMR, infrared, UV-Vis and mass spectrometry) of these compounds can be found in the full paper recently published.28,29


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Scheme 1. Synthesis of 14-aryl-14H-dibenzo[a,j]xanthene derivatives. Among the synthesized materials, three derivatives named XD-01, XD-02, and XD-03 have been chosen as HTM candidates and their molecular structures are shown in Figure 1.

Figure 1. Structure of 14-aryl-14H-dibenzo[a,j]xanthene derivatives used in this work. 2.2. Computational details Charge transport in organic materials rises primarily via hopping mechanism, in which the mobility (μ) of the charge carriers (electrons or holes) is directly proportional to the transfer rate (KCT) of charge carriers (hopping probability per unit time) described by the Einstein relationship:30–33

𝜇=

𝑒𝐴2 2 𝐾𝑏 𝑇

𝐾𝐶𝑇 ,

(Equation 1)



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in which kB, T, e, and A are, respectively, the Boltzmann constant, temperature, elementary charge, and the hopping transport distance. According to Marcus semi-classical model, in organic materials, one of the key parameters that govern the behavior of the charge transfer rate is the reorganization energy (λ) due to the geometric relaxation in the charge transfer.30–32 The charge transfer rate (KCT) may be expressed as follows:32,34 1/2 2𝜋2 𝑎𝑏

𝜋

𝐾𝑐𝑡 = (

𝜆𝐾𝐵 𝑇

)

(

ℎ

−𝜆

)𝑒(

4𝐾𝐵 𝑇

),

(Equation 2)

in which h and are the Planck constant and the electronic coupling matrix element between neighboring interacting molecules, respectively. As it can be seen, λ has a double contribution and it is inversely proportional to the charge transfer rate. As KCT is directly proportional to the charge mobility,32,35 the smaller λ, the better the charge mobility. Assuming that the reorganization energy is dominated by the internal contribution,32,36–38 we can calculate the reorganization energy related to the transport of holes (λhole) through: λhole = [E(1)(M) - E(0)(M)] + [E(1)(M+) - E(0)(M+)], (Equation 3) in which E(0)(M) and E(0)(M+) represent the energy of neutral and cationic states calculated with the respective lower energy geometries, and E(1)(M+) and E(1)(M) represent the energy of cationic in the geometry of the neutral molecule and the energy of neutral molecule in the geometry of the cationic molecule, respectively. λ hole for α-NPD and xanthene derivatives were calculated by using Equation 3. The three structures studied in this paper, neutral and charged, were completely optimized by Density Functional Theory (DFT), employing the Becke three-parameter Lee−Yang−Parr exchange-correlation hybrid functional (B3LYP)39,40 and 6-31G(d,p) basis set.41 The calculus were run with GAUSSIAN09 software.42 This methodology was chosen due its good results and satisfactory accuracy in other studies done with similar materials.37,43–45 The 6 ACS Paragon Plus Environment

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equilibrium geometries were confirmed by vibrational spectrum calculations since no imaginary frequencies were found.

2.3. Structural analysis X-ray powder diffraction (XRPD) analysis were obtained from grounded polycrystalline powder of the XD compounds. Diffraction data were collected by overnight scans (about 14hs) in the 2θ range of 7-105° with steps of 0.02° using a Bruker AXS D8 da Vinci diffractometer, equipped with Ni-filtered CuKα radiation (λ=1.5418 Å), a Lynxeye linear position-sensitive detector. The optics were set up as primary beam Soller slits (2.94°), fixed divergence slit (0.3°), receiving slit (10 mm) and generator at 40 kV and 40 mA. Former unit cell parameters were found using 21 first standard peaks followed by indexing through the single-value decomposition approach46 implemented in TOPAS.47 XD-01 XRPD has been already reported48 and it shows a different molecular packing when compared to XD-02 and XD-03. However, the basic organic compound remains the same in the three compounds. Cell parameters of the three compounds were refined using 7-55 2θ range by Pawley method.49 Then, the structure solution processes were performed by the simulated annealing technique50 also implemented in TOPAS. Each organic molecule was idealized as rigid body model built using Z matrix formalism based on data from single crystals of –H analogous compounds as shown in our previous work.51 Besides the standard distance/angle for aromatic CC and C-H bonds, rotation, translation and torsion angles (see Figure 2) were left free for all rigid body in the simulated annealing step. Final refinements were carried out by the Rietveld.52 It is important to note that the rigid body models introduced at the solution stage were maintained in 7 ACS Paragon Plus Environment


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the final refinement. An isotropic thermal parameter was assigned to all atoms, set at Biso 2.4(0.1) Å2 thermal parameter.

Figure 2. Sketch of a generic XD compound, where R stands for –C(CH3)3 group for XD-02 and –Phenyl group for XD-03. τ1 describes the torsion angle between O-C-C-C. τ2 and τ3 illustrate the free rotation about C-C bonds. The H atoms were omitted for better visualization. 2.4. Optoelectronic and Thermal properties Optical absorption spectra in the UV-Vis range of thermally deposited XD thin films (50nm thick) were obtained with a UV-vis spectrophotometer from SHIMADZU, model UV-1800, using a clean glass substrate as reference. Also, a Synergy H1 (BioTek Instruments) luminescence spectrometer was used to obtain photoluminescence (PL) spectroscopy of the molecules diluted in ethanol. To investigate the thermal properties of the XDs organic compounds, thermogravimetric analysis (TGA) were carried out using a DTG-60 (SHIMADZU). Also, differential scanning calorimetry (DSC) measurements were obtained under nitrogen atmosphere using a DSCQ1000 (TA Instruments). Based on these experiments, thermal parameters such as degradation temperature (Td), glass transition (Tg), crystallization (Tc) and melting temperature (Tm) of the compounds were analyzed. The redox potential of the XD was measured by cyclic voltammeter 8 ACS Paragon Plus Environment

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(CV) with the Ivium Potentiostat system model CompactState using a three-electrode cell equipped with a carbon working electrode, auxiliary platinum wire, and Ag/AgCl pseudoreference electrodes in 0.1 mol.L-1 KCl solution. The electrochemical response of XD was evaluated on modified working electrode53 in which the XD materials were thermally deposited on the surface of the glassy carbon electrode. 2.5. Device Fabrication Electroluminescent devices were fabricated onto an indium-tin-oxide (ITO) coated glass substrate with 15/□ supplied by LUMTEC®. Glass/ITO substrates were previously etched and cleaned with acetone and washed with alkaline detergent. After that, they were sonicated with isopropyl alcohol. Finally, the substrates were treated in an ultraviolet-ozone cleaner chamber. The organic layers were deposited through thermal evaporation in an inert glovebox environment vacuum deposition system at 3 x 10-4 Pa, with a deposition rate of 0.5 and 1.0 Å s-1. The layer thicknesses were controlled in situ through a quartz crystal monitor and confirmed with profilometric measurements. In order to measure the hole mobility of the different HTMs studied in this work, we fabricated devices where the HTL was sandwiched between both electrodes: ITO/HTL (50 nm)/Al (120 nm). We also fabricated some double layer OLED devices with the following architecture: ITO/HTL(50 nm)/Alq3(50 nm)/Al(120 nm), where the xanthene derivatives XD-01, XD-02, XD-03 and the α-NPD were used as HTL. Commercially available (Bis(2-methyl-8-quinolinolate)-4-(phenylphenolato) aluminum) Alq3 was used as an electrontransporting and emissive layer (EML) and aluminum, deposited under same vacuum conditions, was used as cathode. At the same time, a double layer standard device using α-NPD was produced as reference. The fabricated devices had an active area of 4 mm2 and operated in forward bias voltage, with ITO as the positive electrode and Al as the negative electrode. 9 ACS Paragon Plus Environment


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2.6. Device Characterization The electrical and optical properties of the devices were simultaneously recorded with a LabView-based program using a Keithley 2240 current-voltage source, and a calibrated radiometer/photometer (Newport Power Meter, model 1936-c). The electroluminescence spectra were obtained with Ocean-optics USB2000+UV-VIS spectrometer at room temperature without encapsulation. 3. RESULTS AND DISCUSSIONS 3.1. Computational and experimental study of the hole transport properties in XD molecules. Figure 3 presents the final conformation obtained after the geometry optimization from DFT/B3LYP/6-31G(d,p). For the molecule α-NPD (Figure 3a), all the angles between the planes of adjacent rings have values near 50 degrees, due to the repulsion among the hydrogen atoms. The pristine xanthene plane of XD-01 (Figure 3b), XD-02 (Figure 3c) and XD-03 (Figure 3d) slightly bent due to the attached radicals, as it can be observed in Figure 3b, in which it is presented a front view of the XD-01 molecule. Concerning the XD-01 molecule, the aromatic ring bonded to the xanthene stays practically perpendicular to the xanthene plane. While in molecule XD-03, the two aromatic rings linked to xanthene have dihedral angles of about 40º between their planes, due to repulsion between the nearest hydrogen atoms.


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Figure 3. Optimized geometries obtained for (a) α-NPD, (b) XD-01 (left: perspective view; right: front view), (c) XD-02, and (d) XD-03. Table 1 presents the calculated λhole for α-NPD, XD-01, XD-02, and XD-03 using Equation 3. As we can see, all xanthene derivatives have a lower λhole than α-NPD. This suggests that they will present a higher hole mobility than α-NPD. According to our calculations, XD-03 seems to be the best material among the other molecules presented in this work. Indeed, its λhole is the lowest of all the cases studied in the present work. Table 1. Reorganization energy for hole transfer (λhole) obtained for α-NPD, XD-01, XD-02, and XD-03. Structure λhole (meV)

α-NPD 9.083

XD-01 7.277

XD-02 7.040

XD-03 6.723

As mentioned previously, we also experimentally evaluated the hole mobility of each xanthene molecule. The hole mobility (μ0) was determined by fitting the J-V curves to the model of a single carrier space charge limited current (SCLC), which was described by the Mott-Gurney equation: 54–58



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9

𝐽 = 𝜇0 𝜀0 𝜀 8

2 𝑉𝑖𝑛𝑡

𝑑3

𝑒𝑥𝑝 (0.891𝛾√

𝑉𝑖𝑛𝑡 𝑑

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), (Equation 4)

where J is the current density, μ0 is the hole mobility for electric fields tending to zero, d is the hole transport layer film thickness, ε0 is the free space permittivity, and ε is the relative dielectric constant of the studied molecule. In this work, the relative dielectric constant was assumed to be 3.5, as it is typically used for organic semiconducting molecules.56 Vint is the internal voltage and was determined as described in Equation 5: 𝑉𝑖𝑛𝑡 = 𝑉𝑒𝑥𝑡 − 𝑅𝑆 𝐼 − 𝑉𝑏𝑢𝑖𝑙𝑡 , (Equation 5) where Vext is the external voltage applied to the hole transport layer, Rs is an estimative of the series resistance, I is the measured current, and Vbuilt is the built-in voltage. The hole transport mobilities obtained for each material are summarized in Table 2. These results indicate that all XD molecules have a slightly higher hole mobility than α-NPD. Moreover, XD-02 and XD-03 seem to exhibit greater mobilities when compared to the other molecules presented in this work. These results are in agreement with the DFT results previously discussed.


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Table 2. The first set of data shows the hole mobility experimentally evaluated based on a SCLC model for α-NPD, XD-01, XD-02, and XD-03. The other data are published work results that allow a good bibliographic overview of the hole mobility of HTMs as compared to the benzidine family (NBP derivatives).

Characterization method

Material α-NPD

μhole cm2 V-1 s-1

Ref.

1.1 x 10-4

XD-01

SCLC

1.7 x 10-4

XD-02 XD-03

2.0 x 10-4 1.9 x 10-4

α-NPD

5.7 x 10-4

(N,N′-di(naphthalene-1-yl)-N,N′di(phenanthrene-9-yl)biphenyl4,4′-diamine)

TOF / 0.2 MV cm-1

α-NPD

This

work

59

2.2 x 10-4 3.6 × 10-4

H – Tetraarylbenzo [1,2-b:4,5-b’] difurans Me –Tetraarylbenzo [1,2-b:4,5b’]difurans Ph2N – C6H4 –Tetraarylbenzo [1,2b:4,5-b’]difurans (p-tol)2N – C6H4 –Tetraarylbenzo [1,2-b:4,5-b’]difurans

6.4 × 10-4 TOF / 0.25 MV cm-1

8.0 × 10-5

8

2.8 × 10-3 5.6 × 10-4 2.15 10-4

NPB N1,N1,N3,N3-tetra ([1,1′-biphenyl] -4-yl) - N5,N5-diphenyl benzene1,3,5-triamine)

SCLC

6

2.09 10-3 2.15 × 10-4

NPB 2,2′,7,7′ – tetrakis (N, N-carbazole) – spiro (fluorene-9,9′-xanthene) 2,3′,6′,7 – tetrakis (N, N-carbazole) – spiro (fluorene-9,9′-xanthene)

SCLC

9.63 × 10-4

60

1.57 × 10-3



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Table 2 allows to compare the hole mobilities experimentally evaluated for several classes of HTMs. One might keep in mind that the electric properties of organic materials highly depend on the manufacturing process or experimental conditions. On the other hand, the precision of such experimental measurements should fluctuate depending upon the kind of technique used (i.e. time of flight, space charge limited current etc.). This means that a reliable study between the hole transport properties of each organic material should be done through a relative comparison of a given molecule to a well referenced material in the exact same experimental conditions. The bibliographic review shown in Table 2 clearly shows that some HTMs families present hole mobility slightly higher than that of NPB derivatives whenever others tend to decrease depending on the radical attached to the main molecule. Also, few HTMs presented in Table 2 show significant enhancement of the hole mobility by an order of magnitude. This set of data confirms our belief that the type and position of the radicals attached to the main molecule should govern the HTM properties. 3.2. Structural Analysis Crystallographic information of XD-02 and XD-03 compounds are described in Table 3: Main crystallographic characteristics of XD-02 and XD-03.Table 3. XD-02 and XD-03 compounds have the same crystal system/space group: monoclinic and C2/c. Even if they belong to a different crystal system than XD-01, the asymmetric units remain the same. The crystallographic model of XD-03 obtained based on X-ray diffraction experiments is shown in Figure 4. The schematics of XD-01 and XD-02 were omitted here because their structure is very similar to XD-03 where the phenyl group is changed by –H or –C(CH3)3 groups. X-Ray diffraction experiments show that the naphthalene groups in XD-01, -02 and -03 molecules are nearly co-planar, as we have predicted by DFT calculations. Moreover, the diffraction data are in good agreement with the conformation 14 ACS Paragon Plus Environment

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predicted by the DFT geometry optimizations. The angles between the naphthalene groups change slightly when R is –H, –C(CH3)3 and –phenyl, respectively ranging from 177o for XD-01, 181.7o for XD-02 and 179.1o for XD-03. Table 3: Main crystallographic characteristics of XD-02 and XD-03.

Molecular Formula Formula weight (g mol-1) Crystal system Space group a(Å) b(Å) c(Å) β (o) V(Å3) Z Rbragg, Rwp

XD-02 C31H26O 414.57 monoclinic C2/c 23.441(2) 12.002(6) 19.0495(1) 57.35(5) 4512.6(6) 8 0.075, 0.11

XD-03 C33H22O 434.55 monoclinic C2/c 21.143(2) 13.077(1) 18.355(1) 64.61(3) 4584.7(6) 8 0.09, 0.12

Figure 4: Crystal structure of XD-03 drawn using SCHAKAL (Keller, 1986). Carbon, hydrogen, and oxygen atoms were colored as grey, light grey and red, respectively.



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3.3. Optoelectronic Properties The optoelectronic properties of XD compounds are summarized in Table 4. UV–Vis absorption of the thermally deposited thin films are shown in Figure 5. The UV-Vis spectra showed absorption peaks at 220, 245 and 275 nm. Previous works have shown that the absorption spectra of XD molecules diluted in ethanol28 are slightly shifted as compared to the results we obtained. This should be attributed to the packing effect as reported by Surim M. et al61, indicating that there were no molecular structural changes during the thermal evaporation.

Figure 5. (a) Normalized absorption of xanthene derivatives thin films, (b) Normalized absorption and photoluminescence of xanthene derivatives in ethanol solution (1 x 10-6 mol.L-1).

The band gap was calculated from the absorption spectra by measuring the wavelength at which the fundamental absorption occurs (edge of the spectrum) using Tauc plots.62 From these plots we found a Eg  3.5 eV for the three XD compounds. Indeed, all XD compounds do not show any


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absorption band in the visible light region due its wide band gap, and thus they are suitable to be employed as hole injection layer (HIL) and/or hole transporting layer (HTL). Highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels were calculated based on UV-Vis and cyclic voltammetry (CV) results. The voltammogram showed similar trends regarding the onset redox potentials and the oxidation cycles (Figure S1). The oxidation onset potential relative to the SCE of the three compounds was found to be about 1.1 eV, which leads to a HOMO ranging from -5.48 to -5.52 eV. These values are very close to the HOMO level of α-NPD (5.4 eV).59,63 As a consequence, the LUMO energy levels varies from -1.91 to -2.03 eV and was calculated by subtracting the optical bandgap (Eg) from the HOMO value. All the values presented in Table 4 are a definitive evidence that all three XD can be used as a blue emitting layer (EML) as well as a hole transporting layer (HTL). Table 4. Optoelectronic properties of xanthene derivatives. Material XD-01 XD-02 XD-03 α-NPD

λabs max 222 223 215 -

HOMO (eV) -5.48 -5.52 -5.49 -5.40

LUMO (eV) -1.91 -2.03 -1.98 -2.40

GAP (eV) 3.57 3.49 3.51 -

3.4. XD Thermal Stability TGA experiments were carried out under a nitrogen atmosphere with a heating rate of 10 °C/min. Based on the 5-wt.% weight loss (Figure S2) we determined the degradation temperatures of the three XD as follows: 286 °C for XD-01, 328 °C for XD-02 and 340 °C for XD-03. This indicates that these molecules have an excellent thermal stability. DSC measurements were carried out with a first heating/cooling cycle with scanning speed of 10 ºC/min and 50ºC/min respectively, in order 17 ACS Paragon Plus Environment


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to ensure the complete amorphization of the samples. Then, a heating ramp at 10ºC/min was performed and allowed us to determine the glass temperature transition as it can be seen in Figure S3. Analyzing the corresponding data, we obtained a Tg of about 64 ºC for XD-01, 93 ºC for XD02 and 84 ºC for XD-03. The α-NPD Tg is reported around 95 ºC.64,65 This value is higher than the Tg of XD-01. Nonetheless, XD-02 and XD-03 shows similar glass temperatures when compared to the α-NPD one. Thus, we believe that these materials could be used in stable and long lifetime organic electronic devices. Table 5 summarizes all thermal parameters for XD compounds including the melting point temperatures. Table 5. Thermal properties of DX. aGlass Transition (Tg), bCrystallization (Tc), cMelting temperatures (Tm) and dDegradation Temperature. Material

a

b

XD-01 XD-02 XD-03 α-NPD64,65

64 93 84 95

128 126 140 -

Tg (ºC)

Tc (ºC)

c

Tm (ºC)

d

188 298 280 -

268 328 340 310

Td (ºC)

3.5. Device Performances Figure 6(a) shows the electroluminescence spectra of the fabricated devices. The green band centered at 525 nm is typical of Alq3 EL emission. There is a slight enlargement in the Electroluminescent emission when XD molecules are used. It’s worth noting that the device emission band enlargement should not be attributed to the EL emission of xanthenes, considering that Figure 6(a) clearly shows that there is no overlap of the Alq3 and xanthene emission. That should be explained by small structural modifications and morphological differences among the HTL used in this work. This should not be understood as a lower performance of the XD based 18 ACS Paragon Plus Environment

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OLED, but as a change in the (X, Y) color coordinates of the CIE chromaticity diagram (Commission Internationale de l'Eclairage) as shown in Table 6. Figure 6(b) shows the current density-voltage (J–V) curves of all the devices, confirming that they have a typical diode behavior once the current increases exponentially a function of the bias voltage. On the other hand, from the (J–V) curves it is possible to observe that α-NPD reference devices have lower operational voltages when compared to XD ones. Most probably, this should be attributed to variations of hole injection rates at the interface between the anode (ITO) and XD.66–68 Indeed, several studies have shown that the device performances can be increased by using complex multilayer structures (i.e. hole injection layer, hole blocking etc.).69 However, to find out how efficient the XDs materials behave as hole transporting layers we choose to use them in a simple stack bilayer OLED. Figure 6(c) also shows a picture of the XD-03 based device working at 18 V bias voltage.

Figure 6. (a) Normalized EL spectra of the devices (ITO/HTLs/Alq3/Al) at room temperature; (b) The J × V curves of fabricated devices; (c) a picture of XD-03 device under 18V bias voltage. 19 ACS Paragon Plus Environment


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From Figure 7, it is clear that the three devices built with XD compounds as a hole transporting layer showed higher current efficiencies in the range 0-100 mA/cm2 when compared to the reference device. Our theoretical calculations predict that the charge carrier mobility followed the crescent order: α-NPD, XD-01, XD-02, and XD-03. One might expect that this would also be the order of device efficiencies, which is exactly what was obtained in this work. Besides Xanthenes good charge mobility, the high LUMO level act as an Electron Blocking Layer (EBL). The ELB effect prevents electron leaks from EML into the HTL, thus the EML would be the only layer allowed to emit light. XD-03 based devices showed the highest efficiency among all the HTM studied in this work. XD-03 based devices showed a current efficiency of about three times higher when compared to α-NPD ones at 50 mA/cm2. All the presented arguments lead us to believe that we significantly improved the charge balance by using Xanthenes as HTL. The EL performances of the devices are summarized in Table 6.

Figure 7. Current efficiency as a function of the current density of ITO/HTLs/Alq3/Al devices.


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One might question why XD based OLEDs exhibit a lower durability, since xanthenes have a higher degradation temperature, as shown in Table 6. Indeed, degradation mechanisms in small molecule devices is a complex problem to address. It is mandatory to correlate the impact of the device architecture, material properties, manufacturing processes or operating conditions at the same time. For instance, the relationship between the glassy temperature (Tg) and the device stability is still not well understood. Even though it is commonly accepted that molecules with a high Tg are desirable for maximizing OLEDs longevity, Adachi et. al. demonstrated that materials with low Tg might exhibit long lifetimes whenever others with high Tg exhibited shorter lifetimes.70 Moreover, some works pointed out that one of the factors that could influence the degradation process of OLEDs is the interfacial energy between anode and HTL.66,70,71 Finally, we believe that the degradation mechanisms of XD based devices arises from a sum of several effects such as: anode / HT interface energy barrier70, hole injection rates at the interface between the anode and XD72 or hole accumulation in the Alq3/Al interface.

Table 6. The photoelectric properties of devices. HTL

a

V on/off (V)

b

η (cd/A)

c

CIE(X,Y)

XD-01 6.0/15.2 10 (0.26,0.58) XD-02 6.8/30.0 7.2 (0.28,0.57) XD-03 4.5/27.2 16 (0.27,0.58) α-NPD 3.8/13.3 5.7 (0.26,0.29) 2 b a Turn on voltage at 1 cd/m ; current efficiency; at 50 mA/cm2 and c CIE coordinates.



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4. CONCLUSIONS In summary, a novel set of three 14-aril-14H-dibenzo[a,j]xanthene derivative complexes (XD) modified with different functional groups were investigated through the comparison of theoretical calculations and experimental results. Their structures were proposed by theoretical simulations and are in complete agreement with the structures established by state-of-the-art X-ray powder diffraction. DFT results show that xanthene derivatives have a superior hole mobility when compared to the commonly used α-NPD. It appears that XD-03 is the best hole-transporting layer among the three materials studied here. Moreover, we observed that these molecules are thermally and chemically stable. Also, we investigated the influence of XD as hole transporting layer (HTL) on the performance of a simple stack bilayer OLED compared to the reference device fabricated with α-NPD. All XD based devices have improved current efficiency when compared to reference devices. These new HTMs present a low energy barrier between its HOMO levels and the ITO work function. On the other hand, XDs also presents higher LUMO energy, and as a consequence behave as a good EBL. XD compounds are easy to synthesize and exhibit all the qualities required for hole transporting materials. Finally, we expect that these new molecules will be employed in the design of new types of organic optoelectronic devices. 5. ASSOCIATED CONTENT Appendix A. Supporting Information Crystal data, fractional atomic coordinates and displacement parameters of XD-02 and XD-03 structures are supplied in standard CIFs deposited in the Cambridge Crystallographic Data Centre (CCDC

1529653-1529654).

The

data

can

be

obtained

free

of

charge

at 22

ACS Paragon Plus Environment

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http://www.ccdc.cam.ac.uk/conts/retrieving.html [or from Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 (0) 1223-336033; e-mail: [email protected]]. 6. AUTHOR INFORMATION Corresponding Author *[email protected] (J.S.M.) *[email protected] (W.G.Q.) Notes The authors declare no competing financial interest. 7. ACKNOWLEDGMENT This study was supported by Brazilian Agencies CNPq, CAPES, FAPEMIG, FINEP, FAPESP (Procs. 2012/23821-7, 2013/08697-0,

2012/21983-0, 2014/20410-1, and 2016/01599-1),

INCT/INEO and Rede Mineira de Química (RQ – MG) supported by FAPEMIG (Project: REDE113/10; Project: CEX-RED-00010-14). We also thank the Thermal Analysis and Particulate Materials Laboratory (Latep) from National Institute of Metrology, Quality and Technology Inmetro for the DSC analysis. The authors would like to thank Monica Mélquiades for calculating the hole mobility.



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Xanthene derivatives as HTM for Organic Electronic Applications 84x47mm (96 x 96 DPI)

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