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CAPES Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
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 Research Articles
1 1
Charge transport via direct tunneling in 2
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inorganic–organic semiconductor inter- 3
3
S. F. C. Silva, B. S. Zanatta, face in hybrid light emission diodes using

F
4 4
A. C. Rabelo, O. L. Bottecchia, transparent and flexible polyester/copper 5
5
J. R. Tozoni, O. N. Oliveira Jr, selenide (Cu2−XSe) films. is presented. 6
6
A. Marletta*................................2001189

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7 7
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Flexible and Transparent Electrodes
9 9
of Cu2−XSe with Charge Transport via
10 Direct Tunneling Effect 10
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 Research Article

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1
2 Flexible and Transparent Electrodes of Cu2−XSe with Charge 1
2
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Transport via Direct Tunneling Effect 3

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4 4
5 5
6 6
Silésia F. C. Silva, Bruno S. Zanatta, Adriano C. Rabelo, Otávio L. Bottecchia,

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7 7
Q1 8 José R. Tozoni, Osvaldo N. Oliveira Jr, and Alexandre Marletta* 8
9 9
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11 11
12 1. Introduction 12
13 In this paper, it is demonstrated that copper selenide (Cu2−XSe) films onto 13
14 polyester sheets may serve as transparent electrodes in inorganic–organic New generations of organic semicon- 14

PR
15 hybrid light emission devices (IOHLED), as possible replacement to indium ducting devices have driven the search to 15
16 replace the well-established indium-doped 16
tin oxide or fluorine-doped tin oxide. The Cu2−XSe film synthesized via 17
17 tin oxide (ITO) and fluorine-doped tin
18 bath chemical deposition is electrically stable with a sheet resistance of oxide (FTO) electrodes.[1,2] The require- 18
19 148 Ω −1 and optical bandgap of 2.3 eV. IOHLED are made with poly(3,4- ments for alternative materials include a 19
20 ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) as an organic high electrical conductivity and possibility 20
21 layer for hole transport and poly[2-metoxy-5-(2-ethylhexyloxy)-1,4-phenylenev- to prepare thin, transparent and flexible 21
22 films with large areas at low cost. ITO is 22

D
inylene] (MEH-PPV) as electroluminescent semiconductor. The IOHLED
23 used as anode in organic light-emitting 23
24 emits in the visible range owing to the simultaneous emission from Cu2−XSe diodes (OLEDs) due to its transparency in 24
25 and MEH-PPV layers. The enhanced performance is explained by analyzing the visible region and high conductivity 25
26 the charge transport mechanisms at the inorganic–organic interface, which (>103S cm−1). However, the high Schottky 26
TE
27 for Cu2−XSe/PEDOT:PSS changes from Fowler-Nordheim to direct tun- barrier on ITO (or FTO) interfaces makes 27
28 neling regardless of the device temperature (90–370 K). The onset voltage it difficult to inject charge carriers into 28
29 the active semiconducting layer, especially 29
is 75% smaller than in the absence of the PEDOT:PSS layer due to a 27 meV
30 because of its work function of ≈4.4  eV.[3] 30
31 decrease in the potential barrier, and the direct tunneling becomes more This problem can be mitigated by treating 31
32 relevant to device performance than the sheet resistance of the Cu2−XSe layer. its surface to alter the working function or 32
EC

33 Upon adding transparency, mechanical flexibility, and covering large areas, by inserting intermediate layers to change 33
34 the ultrathin Cu2−XSe films on polyester substrates permit new designs for electron mobility and promote a better 34
35 balance between the injected charge car- 35
electro-optical devices with inorganic–organic heterojunctions.
36 riers.[4] Another possibility is to employ 36
37 chalcogenide metals such as copper sele- 37
38 nide that can exist in different composi- 38
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39 tions, namely stoichiometric Cu2Se, Cu3Se2, CuSe, and CuSe2 39

40 and non-stoichiometric Cu2−XSe.[5–9] The latter is a p-type semi- 40
41 conductor with an energy gap of ≈2.3 eV and work function of 41
42 S. F. C. Silva, B. S. Zanatta, Prof. J. R. Tozoni, Prof. A. Marletta 4.17  eV, therefore promising as a hole-injecting electrode for 42
43 Institute of Physics OLEDs.[7,9–11] Films of Cu2−XSe can be prepared with vacuum 43
Federal University of Uberlândia
Q2 44 Uberlândia, MG 38400-902, Brazil evaporation,[12,13] cation-anion combination,[14–16] cation-anion 44
45 E-mail: marletta@ufu.br combination in hot coordinating solvents,[17–19] element com- 45
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46 Prof. A. C. Rabelo bination in the solid state,[20] galvanic synthesis,[21] chemical 46

47 Institute of Science of Education reduction from CuSe,[22] electrochemical methods,[23] and 47
48 Federal University of West Pará chemical bath deposition.[24–26] 48
Caranazal, PA 68040-070, Brazil
49 We demonstrate here that Cu2−XSe films can function as 49
Prof. O. L. Bottecchia
50 Institute of Chemistry
electrodes for organic electronics. The films were synthesized 50
51 Federal University of Uberlândia from copper deposited from the vapor phase followed by chem- 51
52 Uberlândia, MG 38400-902, Brazil ical bath deposition. With polyester as substrate, the resulting 52
53 53
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Prof. O. N. Oliveira Jr films are flexible, thin and transparent. For comparison, devices
54 São Carlos Institute of Physics with an FTO electrode are also discussed. Poly-[2-methoxy-5-(2- 54
55 University of São Paulo ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) was used 55
São Carlos, SP 13560-970, Brazil
56 in a light-emitting inorganic–organic hybrid diode (IOHLED). 56
The ORCID identification number(s) for the author(s) of this article
57 can be found under https://doi.org/10.1002/aelm.202001189.
The effectiveness of Cu2−XSe as electrode was demonstrated in 57
58 a comparison with a device containing an intermediate layer 58
59 DOI: 10.1002/aelm.202001189 of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) 59

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1 shown in Figure S1 in the Supporting Information, for com- 1

2 parison. The ITO substrate has higher transmittance in the vis- 2
3 ible spectrum range above 350 nm, while the transmittance for 3

F
4 CuSe substrates is higher than 80% above 550 nm. Both films 4
5 had significant transmittance in the emission spectral region of 5
6 conjugated and light-emitting polymers (400–750 nm), which is 6

OO
7 of interest to produce displays. For the polyester/Cu2−XSe film, 7
8 light scattering is observed above 350 nm, probably due to the 8
9 film roughness to be discussed later on. The insets in Figure 1 9
10 and Figure S1 (Supporting Information) are the Tauc plots 10
11 according to Equation (1). From the extrapolation of the linear 11
12 region of (αhν)2 versus hν we estimated an optical gap energy 12
13 Eg for FTO and Cu2−XSe as 3.4 and 2.3  eV, respectively, con- 13
14 sistent with the literature.[4,9–11,24,31–34] The bandgap for Cu2−XSe 14

PR
15 is suitable for organic optoelectronic devices. 15
16 Figure 2 shows the AFM images (5.0 µm x 5.0 µm) in the tap- 16
17 Figure 1.  Transmittance spectrum of thin polyester/Cu2−XSe film. The ping mode for polyester, polyester/Cu, and polyester/Cu2−XSe 17
18 inset shows the Tauc plot, from which the bandgap can be calculated films. The image of the glass/FTO substrate is shown in Figure 18
19 using Equation (1). S2 in the Supporting Information. Both polyester and poly- 19
20 ester/Cu are more homogeneous and smoother than polyester/ 20
21 (PEDOT:PSS) between the inorganic and the organic semi- Cu2−XSe and glass/FTO surfaces. The Cu2−XSe film is uniform 21
22 conductor. The devices in this work were designed also to and covers the entire substrate, similar to what is observed for 22

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23 investigate the energy barrier for charge carriers (hole) on FTO. The thickness of the copper and FTO films was obtained 23
24 the Cu2−XSe/MEH-PPV and Cu2−XSe/PEDOT:PSS/MEH-PPV from the AFM measurements (see Supporting Information). 24
25 interfaces. The thickness of the Cu2−XSe film was estimated assuming a 25
26 parabolic growth with coefficients taken from reference 39. The 26
27
TE thickness and mean square roughness (σRMS), skewness (σSK) 27
28 2. Results and Discussion and kurtosis (σKU) parameters for each image in Figure  3 are 28
29 given in Table  1.[35] The values σRMS, σSK, and σKU are similar 29
30 2.1. Gap Energy and Surface Morphology of Cu2−XSe Films for polyester and polyester/Cu, which suggests that the copper 30
31 layer is conformable to the polyester substrate. The parameters 31
32 The optical and morphological properties of Cu2−XSe films for copper selenide were close to those for FTO. In fact, both 32
EC

33 deposited onto polyester sheets were compared with the con- surfaces are similar qualitatively (see Figure  2 and Figure S2 33
34 ventional ITO and FTO electrodes. To analyze the absorption (Supporting Information)). The copper surface changes due 34
35 coefficient (α) and optical energy gap (Eg) of Cu2−XSe films we to a reaction with the selessosulphate ion forming copper 35
36 followed the methodology by Tauc applied to amorphous semi- selenide. The thickness of the initial layer increases with the 36
37 conductor materials,[27–29] using  Equation  (1) for the allowed agglomerates originating from nucleation of multiple clusters. 37
Q3 38 direct transition[4,10,30] The σKU parameter suggests that the peaks on the film surface 38
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39 are sharper than for an FTO film. This can be an advantage to 39

α hν = Ao (hν − E g )
1/2
40 (1) reduce kurtosis (sharpness of the peaks) on the electrodes, an 40
41 effect that decreases the performance of electronic devices in 41
42 where Ao is a proportionality constant and hν is the incident the electrode/semiconductor region. The parameter σSK indi- 42
43 photon energy.[28] Figure  1 shows the transmittance spectrum cates that the Cu2−XSe surface has more peaks than valleys. 43
44 of the polyester/Cu2−XSe film at room temperature. The trans- The height distribution function p(h), where h is the height 44
45 mittance spectrum and Tauc plot of the glass/FTO film are along the surface, has a Gaussian profile for FTO and Cu2−XSe 45
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59 Figure 2.  AFM images of a) polyester, b) polyester/Cu, and c) polyester/Cu2−XSe. 59

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1 FTO or ITO in the market, with the advantage of grain shapes 1

2 that affect the conductivity. Furthermore, it is suitable for adhe- 2
3 sion of the organic semiconducting layer. 3

F
4 4
5 5
6 2.2. Electrical Analysis of the IOHLEDs 6

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7 7
8 We used the four-point methodology to determine the sheet 8
9 resistance (Rs) and electrical resistivity (ρ) of FTO, Cu and 9
10 Cu2−XSe.[36,37] The details of layout and parameters are given in 10
11 the Supporting Information. A constant electric current of 1 mA 11
12 was used. The results for FTO agree with the data provided by 12
13 the manufacturer with Rs of 14.6 Ω −1,[32] while the average of Rs 13
14 for copper selenide was 148.8 Ω −1, compatible with applications 14

PR
15 in electronic devices.[38,39] In subsidiary experiments with 100 15
16 repeated bending cycles (0–170°), we obtained an average value 16
17 Figure 3.  I versus F characteristic curve of IOHLEDs with PEDOT:PSS
of 148 ± 5 Ω −1 for Rs of Cu2−XSe films, according to the results 17
18 (red) and without PEDOT:PSS (black). in Figure S8 in the Supporting Information. Figure 3 shows the 18
19 characteristic curves of I versus F (electric field) of IOHLEDs at 19
20 films, with the profile for Cu2−XSe film being 35% narrower. room temperature. The threshold voltages differ in the poten- 20
21 The height profile of copper resembles that of polyester. tial range studied with significant carrier injection in the device 21
22 Overall, we may consider all samples as having a random dis- with PEDOT:PSS (5 MV m−1). This should lower the potential 22

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23 tribution of heights. The increase in mean quadratic rough- barrier at the junction compared to the IOHLED without the 23
24 ness for Cu2−XSe indicates a larger height dispersion on the PEDOT:PSS layer (21.7 MV m−1). The magnitude of the electric 24
25 film surface. The histograms of area distribution for the cross current in these devices is as expected from the literature.[35,36] 25
26 section of polyester/Cu2−XSe and Glass/FTO are given in Note that for conventional OLEDs, for example FTO/PSS:MEH- 26
TE
27 Figure S3 (Supporting Information), with circular clusters for PPV/Al, the threshold voltage is ≈80 MV m−1.[40] Hence, despite 27
28 Cu2−XSe and rectangular clusters for FTO. The average areas of the increased sheet resistance of the Cu2−XSe layer in compar- 28
29 the grain section are 38713 and 20715 nm2 for Cu2−XSe (average ison with conventional electrodes, the decrease in the energy 29
30 radius of 160  nm) and FTO (length of 312  nm and width of barrier at the inorganic–organic semiconductor junction can be 30
31 123 nm), respectively. These data are consistent with the lowest significantly more effective in the charge transport along the 31
32 σRMS for Cu2−XSe and reflect the large difference in mor- IOHLED layers. The electrical device stability was verified with 32
EC

33 phology between FTO and Cu2−XSe surfaces. Table SI1 in the 120 consecutive scans polarizing directly the IOHLEDs devices 33
34 Supporting Information presents the parameters hc (center) (Figure S9 in the Supporting Information). No change was 34
35 and Δh (width) of the Gaussian fitting of p(h) for the images observed in the I versus V curves after the 60th scan. 35
36 in Figure 2 and Figure S3 (Supporting Information). The self- The results in Figure  3 represent a demonstration that effi- 36
37 correlation image between heights in Figure S4 (Supporting cient IOHLEDs may be obtained with Cu2−XSe in the trans- 37
38 Information) was obtained using the second order statistical parent electrode and a PEDOT:PSS layer for hole injection. 38
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39 model,[35] where light regions indicate patterns of distances Furthermore, one infers that it is also possible to fabricate a 39
40 with most correlated heights. The correlation for polyester hybrid LED without a PEDOT:PSS layer, but then the electron- 40
41 has a groove pattern probably due to the lamination used in injecting layer should be improved for both devices. In order 41
42 the industrial process, and this pattern is followed by depos- to propose new designs, we investigated the charge transport 42
43 ited copper. This pattern disappears after the chemical reac- and interfacial mechanisms in inorganic/organic layers, as dis- 43
44 tion in the Cu2−XSe synthesis process with the film growing cussed next. 44
45 in a more isotropic manner, similarly to FTO (see Figure S4 in Three main charge transport mechanisms are involved on 45
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46 the Supporting Information). We may conclude that Cu2−XSe the interfaces of these devices. The first includes the Schottky 46
47 grows by homogeneous random nucleation and non-correlated barrier (BS) formed at the interface between a metal and a 47
48 throughout the Cu film. This morphology is similar to those of semiconductor owing to the difference in work functions. 48
49 The second mechanism is the Fowler-Nordheim (FN) process, 49
50 Table 1.  Thickness, mean quadratic roughness, skewness and kurtosis which manifests itself at low temperatures and high electric 50
51 of Glass/FTO, polyester, polyester/Cu, and polyester/Cu2−XSe. fields. The third is direct tunneling (DT), significant at small 51
52 electric fields because carrier injection depends exponentially 52
53 σRMS [nm] σSK σKU on the difference in carriers energy and potential energy at 53
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Sample Thickness [nm]

54 Glass/FTO 350 ± 4 17.2 0.2 2.8 the semiconductors interface.[41] In the devices studied here, 54
55 Polyester – 2.0 1.0 9.0 the Schottky barrier (BS) is formed on the electrode/polymer 55
56 interface (MEH-PPV/Al) due to the difference between the 56
polyester/Cu 43 ± 5 2.5 0.8 6.8
57 energy levels, increasing contact resistance and being rectified 57
58 Polyester/ 140 11.3 0.4 3.5 with the application of a polarization voltage. The injection of 58
Cu2−XSe
59 charge carriers into organic films occurs through tunneling and 59

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1 thermionic emission mechanisms. The equations for direct tun- the characteristic curve had its shape altered slightly with the 1
2 neling (DT) and Fowler-Nordheim (FN) are, respectively[7,41–43] temperature for the PEDOT:PSS device. The change in electrical 2
3 current with increasing temperature is due to the thermal acti- 3

F
4 I 1  2 2m eff φ 1/2  vation of charge carriers, with the results for the device without 4
5 ln  2  ∝ ln   −   (2) PEDOT:PSS being in accordance with the literature.[44] Figure  4 5
F  F  
6 shows the tunneling plot for both devices from 90 to 370 K. Dif- 6

OO
7 I 1  4 2m eff φ 3/2  ferent charge injection behaviors through the inorganic–organic 7
8 ln  2  ∝ −   (3) semiconductor interfacial barrier are identified. FN and DT 8
F  F 3e
9 tuning occur in the device without PEDOT:PSS and DT occurs 9
10 where I is the electric current, F is the electric field, ϕ is the only in the device with PEDOT:PSS. A detailed analysis of the 10
11 height of the barrier, meff is the effective mass of the holes Cu2−XSe/MEH-PPV interface shows a non-linear increase in the 11
12 injected into the polymer layer, e is the electron charge, h region of lower polarization, which reveals an FN to DT transi- 12
13 is the Planck’s constant, and the thickness of the thin barrier tion. In contrast, the Cu2−XSe/PEDOT:PSS/MEH-PPV device 13
14 is 1 nm.  Note that DT occurs when the applied bias voltage is shows increasing curves over the polarization interval, which 14

PR
15 less than the average barrier height and FN occurs if the bias indicates a dominating DT mechanism. When a lower polariza- 15
16 voltage exceeds that barrier. FN tunneling is a consequence of tion is applied to the Cu2−XSe/MEH-PPV contact in Figure  4a, 16
17 reducing the width of the barrier. carriers have to overcome a wide barrier (rectangular barrier) and 17
18 Electrical measurements were performed at various tempera- charge transport takes place via DT. This result indicates that the 18
19 tures to examine the competition between thermionic emission DT effect is more important than the sheet resistance of the CuSe 19
20 and charge transport via tunneling, and the I versus V curves are layer, i.e., the relevant physical parameter is the decrease in the 20
21 shown in Figure S9 in the Supporting Information. The device potential energy barrier at the inorganic/organic interface. For 21
22 without PEDOT:PSS had a distinctive characteristic curve at such a decrease allows for considerable carrier injection in the 22

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23 higher temperatures, with an increased electric current. However, device when the electrode is a p-type inorganic semiconductor. 23
24 At a higher polarization, the energy barrier reduces, becoming 24
25 thin and approximately triangular, increasing the probability of 25
26 FN tunneling. Therefore, there is a change in transport mecha- 26
27
TE nism from DT at the smallest polarization (or larger 1/F) to FN at 27
28 the highest polarization (smallest 1/F). The intersection occurs at 28
29 0.026 m MV−1 at an ambient temperature of 290 K and at 0.07 m 29
30 MV−1 for the higher temperatures of 330 and 370 K. The crossing 30
31 point is known as the transition voltage (Vtrans). Figure S10 in the 31
32 Supporting Information shows details of the transition of the two 32
EC

33 regimes for the polyester/Cu2−XSe/MEH-PPV/Al device. 33

34 Two factors compete to determine how the tunneling plot 34
35 changes with temperature in Figure  4, which can be detected 35
36 at lower polarizations. The first relates to the vibrational levels 36
37 of the polymer, which become more accessible with increasing 37
38 temperatures (charge carriers have more energy to jump over 38
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39 barriers on the interfaces). The second is the aforementioned 39

40 vacancy defects (traps) in Cu2−XSe, where the charge car- 40
41 riers are susceptible to being trapped. In the device without 41
42 PEDOT:PSS in Figure 4a the access to the vibrational levels of 42
43 the polymer increases with temperature, while trapping due 43
44 to Cu2−XSe defects decreases. In the device with PEDOT:PSS 44
45 in Figure  4b, the two processes occur equally, one compen- 45
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46 sating the other. Therefore, the values of electric current for 46

47 this sample vary little with temperature as shown in Figure 47
48 S9d in the Supporting Information. At low temperatures, we 48
49 observed only DT in the device without PEDOT:PSS. With less 49
50 thermal energy, the charge carriers are less likely to overcome 50
51 the energy barrier on the interface. Therefore, the low tempera- 51
52 ture mechanism is tunneling. The transition from DT to FN 52
53 occurred only at temperatures 290, 330, and 370 K. We do not 53
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54 rule out the mechanism via hopping because the crossing point 54
55 between the two tunneling processes varies. This transition 55
56 occurs at lower voltages at higher temperatures (330 and 370 K). 56
Figure 4.  Tunneling plots (Equations  (2 and  3)) for IOHLED samples
57 at various temperatures, from 90 to 370 K: a) without PEDOT:PSS and We estimate the barrier height, ϕ, at 27 meV based on the FN 57
58 b) with PEDOT:PSS. The insets show a zoom in the high field region and tunneling equation. We assume the linear dependence in the 58
59 dashed lines indicate the transition from DT to FN mechanisms. higher field interval (≈30  V m−1) and the effective mass of the 59

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1 assume that for the IOHLED Cu2−XSe/MEH-PPV/Al there is an 1

2 interface region creating a small barrier, originated in the inter- 2
3 stitial defects of Cu2−XSe. In the Cu2−XSe/PEDOT:PSS junction, 3

F
4 the residual charges of the organic layer should passivate the 4
5 surface of the inorganic semiconductor. 5
6 6

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7 7
8 2.3. Electroluminescence of the IOHLEDs 8
9 9
10 Electroluminescence is observed only with the device without 10
11 PEDOT:PSS after the stability test (after 120 scans), as shown 11
12 in Figure S9 in the Supporting Information. Probably, the hole 12
13 Figure 5.  Energy diagrams for IOHLED polyester/Cu2−XSe/MEH-PPV/Al injection through the PEDOT:PSS layer is higher than the elec- 13
14 (left) and polyester/Cu2−XSe/PEDOT:PSS/MEH-PPV/Al (right). tron injection provided by aluminum, resulting in the imbal- 14

PR
15 ance of electron-hole pairs required in the active layer for light 15
16 holes as, approximately, the mass of the free electron ( meff  = emission. Figure  6 shows the normalized photoluminescence 16
17 m0 ). This relatively low value indicates the compatibility of the spectra of MEH-PPV, polyester/Cu2−XSe and polyester/Cu2−xSe/ 17
18 energy levels of Cu2−XSe and MEH-PPV. In the PEDOT:PSS MEH-PPV films excited at 405  nm at room temperature. It is 18
19 device there is no evidence of FN tunneling, demonstrating worth noting that the presence of PEDOT:PSS does not change 19
20 that the decrease in the energy barrier is insignificant even at the emission spectrum (not shown) of polyester/PEDOT:PSS/ 20
21 high fields. Cu2-xSe/MEH-PPV film. The optical absorption spectra of these 21
22 On the interface of a p-type semiconductor (Cu2−XSe) with an films are shown in Figure S11 in the Supporting Information. 22

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23 intrinsic semiconductor (MEH-PPV), there is a discontinuity in Two characteristic peaks of the MEH-PPV polymer represent 23
24 the energy bands due to the reorganization of the charge car- the emission of zero phonon at 588  nm (transition 0–0) and 24
25 riers. Discontinuity represents a barrier that hinders carrier the first phonon replica at 632  nm (transition 0–1), and there 25
26 diffusion from Cu2−XSe to MEH-PPV. An energy barrier also is an emission band of the Cu2−XSe at 504  nm. The emission 26
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27 exists in the Cu2−XSe/PEDOT:PSS/MEH-PPV device. However, spectrum of the polyester/Cu2−XSe/MEH-PPV sample shows 27
28 PEDOT:PSS favors hole injection in the active layer. In both the overlap of both emission bands of Cu2−XSe and of MEH- 28
29 devices, the energy barrier is a consequence of intrinsic defects PPV semiconductors. The electroluminescence spectrum (15 V 29
30 such as vacancies of non-stoichiometric compounds like at room temperature) is also shown in Figure  6 for the device 30
31 Cu2−XSe, causing a charge decompensation. The traps make it without PEDOT:PSS. We identified two peaks from the emis- 31
32 difficult to inject holes in MEH-PPV, contributing to the bal- sion of Cu2−XSe at 504  nm and zero phonon emission from 32
EC

33 ance of charge carriers. The PEDOT:PSS layer causes passiva- MEH-PPV at 578 nm. The third peak at 637 nm represents the 33
34 tion of the copper selenide surface, minimizing the interaction first phonon replica of MEH-PPV. The line intensity at 637 nm 34
35 of Cu2−XSe defects in the charge injection process. This explains increased substantially for the electroluminescence spectrum 35
36 the difference in behavior of the devices analyzed. The energy probably due to the self-absorbing effect of the light transmitted 36
37 band diagram models proposed in Figure  5 are approximate through the Cu2−XSe layer. This can be controlled if we change 37
38 models, since intrinsic defects in Cu2−XSe are neglected. The the thickness of each active layer, thus introducing another 38
RR

39 values of LUMO and HOMO energies for Cu2−XSe films are parameter to adjust the spectral emission center of the device. 39
40 -4.4 and -6.6eV,  respectively.[4,45] Based on our results, we can An important feature to be highlighted is the wide emis- 40
41 sion spectrum for the IOHLED upon combining emitting 41
42 inorganic and organic semiconductors, with the inorganic one 42
43 also serving as hole transporting layer. Since this latter layer of 43
44 Cu2−XSe is transparent and flexible, it may replace ITO or FTO. 44
45 Table  2 lists transparent oxides, graphene, carbon nanotubes, 45
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46 composites, and conducting polymers used in p-type hole 46

47 injecting electrodes. Useful characteristics of the electrodes are: 47
48 transparency above 60% in the visible region (≈500 nm), sheet 48
49 resistance ≈100 Ω −1, mechanical flexibility, even when synthe- 49
50 sized with different techniques. Also in Table 2 is a comparison 50
51 of physical properties of Cu2−XSe and other electrode materials, 51
52 with chemical bath deposition being the technique that permits 52
53 53
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large area applications.

54 54
55 55
56 3. Conclusions 56
Figure 6.  Continuous line: IOHLED EL spectrum of polyester/Cu2−XSe/
57 MEH-PPV/Al operating at 15 V. Dashed lines: photoluminescence spectra 57
58 of Cu2−XSe and MEH-PPV semiconductors excited at 405  nm at room Copper selenide is stable and can be used as a hole injector 58
59 temperature. electrode in IOHLEDs devices in the form of thin transparent 59

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1 Table 2.  Comparison of electrodes for OLED applications. flexible films. The following characteristics were determined 1
2 for 140  nm thick films: bandgap energy of 2.3  eV, edge of the 2
3 Electrode Properties absorption band close to 450 nm, maximum photoluminescence 3

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4 Cu2−XSe [48–50]
Optical bandgap ≈ 2.3 eV spectrum at 504 nm (excitation at 405 nm) and sheet resistance 4
5 Sheet resistance ≈ 148 Ω −1 of 148 Ω −1. The roughness and homogeneity are comparable to 5
6 Transmittance ≈ 50–60% those of commercially-acquired FTO films, with the advantage 6

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7 σRMS ≈ 11.3 nm that its morphology can favor reduction of the tip effects and 7
8 Flexibility: yes the accumulation of charge in small regions of the electrode. In 8
9 Synthesis: Chemical Bath Deposition (CBD) the Cu2−XSe/MEH-PPV/Al IOHLED there is a transition from 9
10 Transparent conduc- Optical bandgap ≈ 3.5 eV tunneling FN to DT, with a barrier height of 27 meV. With the 10
11 tive oxides: ITO, FTO, Sheet resistance ≈ 20–36 Ω −1 addition of an intermediate layer of PEDOT:PSS hole carrier, 11
12 ZnO, InZnO, ZTO, Transmittance ≈ 95% the IOHLED featured only the DT charge injection mechanism. 12
[1,2,51]
13 TiO2, MoO σRMS ≈ 17.2 nm This explains the considerable decrease in its operating voltage, 13
Flexibility: no
14 demonstrating that even under high electric fields there is no 14

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Synthesis: radiofrequency (RF) sputtering
15 significant reduction in the energy barrier. As a result, the 15
[52]
16 Graphene Optical bandgap ≈ 4.7 eV direct tunneling in the Cu2−XSe/PEDOT:PSS interface allows 16
Sheet resistance ≈ 43 Ω −1
17 for a low operating voltage in the device, despite the increased 17
Transmittance > 97.7%
18 sheet resistance. In both devices the charge transport mecha- 18
Flexible: yes
19 Synthesis: Chemical Vapor Deposition (CVD) on Cu foil
nism via hopping must occur along with the tunneling mecha- 19
20 nism in these interfaces. The PEDOT:PSS device did not show 20
Graphene/MoO3[53] Optical bandgap ≈ 2.8 eV
21 detectable electroluminescence in our experimental apparatus, 21
Sheet resistance ≈ 100–200 Ω −1
22 probably due to the significant imbalance of charge injection. 22

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Transmittance ≈ 90%
23 Flexibility: yes In the device without PEDOT:PSS, the EL curve shows a red 23
24 Synthesis: low-pressure CVD shift in relation to the PL spectrum. While the wide emission 24
25 spectrum is not suitable for emission of pure colors, it creates 25
Graphene/TiO2[54–56] Optical bandgap ≈ 2.4 eV
26 the opportunity to fabricate devices for lighting. Its emission 26
27
TE Sheet resistance ≈ 93 Ω −1
Transmittance ≈ 90% region may be possibly controlled by changing the thickness 27
28 Flexibility: no (rigid glass substrate) of the Cu2−XSe layer or the organic active layer. The optical 28
29 Synthesis: DC pulsed (500 W) or RF (120 W) and electrical results are demonstration of the possible use of 29
30 sputtering process on single-layer graphene on a Cu Cu2−XSe films as transparent, flexible electrodes in hybrid light- 30
31 foil and subsequent wet-transfer process to a target emitting devices processed at low cost and large areas. 31
32 substrate 32
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33 Graphene/Ag Optical bandgap ≈ 4.9 eV 33

34 nanowire[57,58] Sheet resistance ≈ 26.4 Ω −1
4. Experimental Section 34
35 Transmittance ≈ 91.5% 35
36 σRMS ≈ 6.4 nm Cu2−XSe Films: Cu2−XSe substrates were obtained by evaporating 36
Flexibility: no (rigid glass substrate) a thin (< 50  nm) layer of copper onto a transparent polyester sheet
37 37
Synthesis: CVD (polyester film for inkjet printers, thickness ≈ 100 µm) under a vacuum
38 of ≈8 × 10−3 mbar. A sodium selenosulfate (Na2SeSO3) stock solution 38
Optical bandgap ≈ 4.1 eV
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39 Carbon Nanotubes was prepared.[46] This reactant cannot be isolated in the pure state, 39
40 (CNT)
[59]
Sheet resistance ≈ 100 Ω −1 but it can be kept stable for several months in aqueous 0.10  mol L−1 40
Transmittance ≈ 90% Na2SO3. A mixture of selenium (5  g), Na2SO3 (12  g) and ultrapure
41 41
Flexibility: no (rigid glass substrate) water (150  mL) was boiled for 12 h using a condenser to prevent loss
42 42
Synthesis: micro-contact printing CNT films with of solvent. The mixture was left to rest for several hours at room
43 polydimethylsiloxane (PDMS) stamp
43
temperature, and residues were discarded. The actual concentration in
44 the clear solution was determined by gravimetry. An aliquot (5  mL) of 44
Single-Wall Carbon Optical bandgap ≈ 4.7 eV
45 the stock solution was decomposed with concentrated HCl. Selenium 45
Nanotube (SWNT)[60] Sheet resistance ≈ 60 Ω −1
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46 Transmittance ≈ 45%
precipitates were filtered, washed, dried and weighed (0.039 g). For the 46
47 chemical bath deposition, the stock solution was diluted to 8.0 mmol L−1 47
Flexibility: no
48 with 0.10  mol L−1 Na2SeSO3, where the copper/polyester substrate was 48
Synthesis: pulsed laser vaporization technique
49 SWNT/PEDOT[61] immersed for 1  min to 2  min under magnetic stirring. After removal, 49
Optical bandgap ≈ 1.6 eV it was washed with ultrapure water. X-Ray diffraction (XRD) and energy
50 Sheet resistance ≈ 160 Ω −1 dispersive X-ray spectroscopy (EDS) were carried out using, respectively,
50
51 Transmittance ≈ 86% a diffractogram X-Ray Shimadzu XRD6000 and a Tescan Vega 3 LMU. 51
52 Flexibility: yes XRD and EDS curves typical of berzelianite phase are shown in Figures 52
53 S12 and SI3, respectively, in the Supporting Information.[7,47] 53
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Synthesis: in situ polymerization of PEDOT on

54 poly(ethylene naftalina)/SWNT Light Emitting Diodes with Inorganic–Organic Multilayers: The 54
55 Polyethylene substrates containing copper selenide were cleaned with ultrapure 55
Optical bandgap ≈ 2.5 eV
water and detergent. Figure 7a depicts the film thus obtained. A nickel-
56 Terephthalate/ Transmittance > 70% 56
plated copper wire was used as electrical contact on the copper selenide
57 polyaniline:camphor Sheet resistance ≈ 100 Ω−1 electrode (anode). Silver glue and epoxy glue were used to cover, insulate 57
58 sulfonic acid (PET/ Flexibility: yesSynthesis: spin-cast film of dissolved in and protect the contact. Spin-coating was employed to prepare the active 58
[52]
59 PANI:CSA) m-cresol PANI:CSA on PET sheet layer of MEH-PPV from a 3.3 mg mL−1 solution in chloroform (Aldrich).[40] 59

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2 2
3 3

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4 4
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6 6

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7 7
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9 9
10 10
11 Figure 7.  a) Photograph of the polyester/Cu2−XSe film. Schematic architecture of IOHLEDs: b) polyester/Cu2−XSe/PEDOT:PSS/MEH-PPV/Al and c) 11
12 polyester/Cu2−XSe/MEH-PPV/Al. 12
13 13
14 14
The final film thickness was ≈200 nm. The rotation speed was 1400 rpm Received: December 4, 2020

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15 for 60 s under a relative humidity of 20%. A second device was made Revised: March 2, 2021 15
16 by interposing a hole injection layer of PEDOT:PSS (Sigma-Aldrich), Published online: 16
17 which was deposited by spin coating at 3000  rpm for 60 s from a 1.3% 17
18 dispersion in chloroform. The sample was then heated under vacuum at 18
19 120 °C for 1 h. Finally, aluminum was evaporated under vacuum of ≈8 × 19
10−3 mbar and the active area of the devices was 7.1 mm2. Figure  7b,c [1] H.  Kim, C. M.  Gilmore, A.  Piqué, J. S.  Horwitz, H.  Mattoussi,
20 20
shows the IOHLED architectures which is referred to as Cu2−XSe/ H.  Murata, Z. H.  Kafafi, D. B.  Chrisey, J. Appl. Phys. 1999, 86,
21 PEDOT:PSS/MEH-PPV/Al and Cu2−XSe/MEH-PPV/Al, respectively. 21
22 6451. 22
Device Characterization: Optical absorption measurements were

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[2] A. E. Rakhshani, Y. Makdisi, H. A. Ramazaniyan, J. Appl. Phys. 1998,
23 performed using the UV-VIS 800XI Femto spectrophotometer and 23
83, 1049.
24 surface morphology was studied using an atomic force microscope 24
[3] A. C. Rabelo, A. Marletta, R. A. Silva, N. M. B. Neto, O. L. Bottecchia,
25 (AFM) Shimadzu SPM-9600. For continuous current (CC) four-probe 25
electrical measurements, a Keithley 2410-C voltage source was used. Synth. Met. 2009, 159, 2318.
26 26
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Photoluminescence spectra were obtained using the Laser Line iZi as [4] N.  Thejo Kalyani, S. J.  Dhoble, Renewable Sustainable Energy Rev.
27 the excitation source at 405 nm, and the light emitted by the sample was 2012, 16, 2696. 27
28 guided by a set of biconvex lenses and detected with a portable USB4000 [5] H.  Hiramatsu, I.  Koizumi, K.-B.  Kim, H.  Yanagi, T.  Kamiya, 28
29 spectrometer from Ocean Optics. A 450  nm cutoff high-pass filter was M.  Hirano, N.  Matsunami, H.  Hosono, J. Appl. Phys. 2008, 104, 29
30 placed in front of the spectrometer to cut the corresponding excitation 113723. 30
31 wavelength. In the electroluminescence measurements, a Keithley [6] K. Tyagi, B. Gahtori, S. Bathula, S. Auluck, A. Dhar, Appl. Phys. Lett. 31
32 2410-C source was as CC source and the emitted light was collected 2014, 105, 173905. 32
EC

and detected as described above. Conductivity measurements in CC [7] S. R. Gosavi, N. G. Deshpande, Y. G. Gudage, R. Sharma, J. Alloys
33 33
condition were performed at various sample temperatures (90–370 K) Compd. 2008, 448, 344.
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39 Innov. 2013, 2, 82. 39

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46 [16] H.  Pathan, C.  Lokhande, D.  Amalnerkar, T.  Seth, Appl. Surf. Sci. 46
The authors acknowledge the financial support from the Brazilian
47 agencies CNPq (424338/2018-1 and 302224/2018-1), CAPES, FAPEMIG, 2003, 211, 48. 47
48 and FAPESP (2018/22214-6). [17] S.  Deka, A.  Genovese, Y.  Zhang, K.  Miszta, G.  Bertoni, R.  Krahne, 48
49 C. Giannini, L. Manna, J. Am. Chem. Soc. 2010, 132, 8912. 49
50 [18] C.-T. Yang, H.-I. Hsiang, Mater. Res. Bull. 2018, 97, 30. 50
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Conflict of Interest 2010, 22, 3586. 52
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The authors declare no conflict of interest.

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59 injector electrode, inorganic–organic light emission diodes [24] V. Garcı́a, P. Nair, M. T. Nair, J. Cryst. Growth 1999, 203, 113. 59

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34 Silésia F. C, Silva, Institute of Physics, Federal University of Uberlândia, Brazil Silésia de Fátima 34
35 Curcino da Silva has a MSc in Physics from the Federal University of Uberlândia (UFU), Brazil, 35
36 working on electrical properties of organic field effect transistors. She obtained a PhD degree 36
37 in 2016 from the same university with a study of the performance of PLEDs. She completed 37
38 postdoctoral research in copper selenide electrodes in 2018, and is a lecturer at UFU. She is the 38
author of 8 publications, and has experience in polymers and their applications in organic elec-
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39 39
40 tronic devices and periodic 2D nanostructures using lithography techniques. 40
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Bruno S. Zanatta, Institute of Physics, Federal University of Uberlândia, Brazil Bruno Souza
47 47
Zanatta received his BSc from the Federal University of Uberlândia, Brazil, working on using
48 48
Arduino to automate the release of curcumin. He is currently a MSc student at the same univer-
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sity, working on organic light-emitting devices under the supervision of Prof. Alexandre Marletta.
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2 Adriano C. Rabelo, Institute of Science of Education, Federal University of West Pará, Brazil 2
3 Adriano C. Rabelo has a BSc and MSc in Chemistry from the Federal University of Uberlândia, 3

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4 Brazil, working on metallic chalcogenides for solar cells, LEDs, catalysis, photocatalysis, electro- 4
5 catalysis. He obtained a PhD degree in 2001 from the Federal University of São Carlos, Brazil, 5
6 with the synthesis and characterization of Pt-TiO2 nanoparticles. Then moved to Institute of 6

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7 Science of Education, Federal University of West Pará, Brazil in 2017. He has expertise on optical 7
8 spectroscopy, electro- and photo-chemistry, and impedance spectroscopy. 8
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16 Otávio L. Bottecchia, Institute of Chemistry, Federal University of Uberlândia, Brazil Otávio Luiz 16
17 Bottecchia teaches at the Chemistry Institute of Federal University of Uberlândia since 1989 and 17
18 wrote papers on thin films, chemical kinetics, and experimental physical chemistry. 18
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José Roberto Tozoni, Institute of Physics, Federal University of Uberlândia, Brazil José Roberto
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Tozoni received his PhD (2009) from University of São Paulo, Brazil, working on Zero-Field NMR
31 31
of Magnetic Materials. In 2010, he became a professor at Physics Institute, Federal University of
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Uberlandia, Brazil. His research interests concern development of organic/organic or organic/

33 33
inorganic systems which promote the deaggregation of organic dyes and the study of photophys-
34 34
ical, photochemical, structural and functional properties of these systems.
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42 Osvaldo N. Oliveira Jr., São Carlos Institute of Physics, University of São Paulo, Brazil Osvaldo 42
43 N. Oliveira Jr. is a professor at the São Carlos Institute of Physics, University of São Paulo, Brazil, 43
44 having obtained his PhD from Bangor University in 1990. He is a member of the Latin American 44
45 Academy of Sciences, a former president of the Brazilian Materials Research Society, and execu- 45
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46 tive editor of ACS Applied Materials & Interfaces. Prof. Oliveira has led research into novel 46
47 materials and has pioneered the combined use of statistical physics and artificial intelligence to 47
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2 Alexandre Marletta, Institute of Physics, Federal University of Uberlândia, Brazil, Brazil Alexandre 2
3 Marletta received his BSc and MSc in Physics from the University of São Paulo, Brazil, working 3
on theory of electronic structure of inorganic semiconductors. He obtained a PhD degree in 2001

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5 from the same university in photophysical properties of conjugated luminescent polymers. He 5
6 then moved to Uberlandia Federal University, Brazil, as professor in the Institute of Physics in 6

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7 May of 2002. In 2003 he created the Materials Spectroscopy Group and he is the author of over 7
8 110 publications, related to theory and experiments in electronic-vibrational spectroscopy. He has 8
9 expertise on spectroscopy of organic materials, thin-film processing and organic electronics. 9
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