INORGANIC-ORGANIC FILM FOR CONDUCTIVE, FLEXIBLE, AND TRANSPARENT ELECTRODES
20210135056 · 2021-05-06
Inventors
Cpc classification
H01L21/02118
ELECTRICITY
H01L31/1884
ELECTRICITY
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H10K85/1135
ELECTRICITY
International classification
H01L31/18
ELECTRICITY
Abstract
An electrode includes a polymer based substrate; a polymer based buffer layer, wherein the polymer buffer layer includes a first polymer that is doped with a second polymer and further includes a polar solvent to increase its electrical conductivity; and a conducting film formed on the polymer based buffer layer, the conducting film being transparent to visible light. The electrode is flexible, electrically conductive and transparent to the visible light.
Claims
1. An electrode comprising: a polymer based substrate; a polymer based buffer layer, wherein the polymer buffer layer includes a first polymer that is doped with a second polymer and further includes a polar solvent to increase its electrical conductivity; and a conducting film formed on the polymer based buffer layer, the conducting film being transparent to visible light, wherein the electrode is flexible, electrically conductive and transparent to the visible light.
2. The electrode of claim 1, wherein the polymer based substrate is made of polyethylene terephthalate (PET).
3. The electrode of claim 2, wherein the first polymer of the buffer layer is polymer poly-(3,4-ethylenedioxythiophene) (PEDOT).
4. The electrode of claim 3, wherein the second polymer of the buffer layer is poly-(styrenesulfonic acid) (PSS).
5. The electrode of claim 4, wherein the polar solvent is ethylene glycol (EG).
6. The electrode of claim 5, wherein the conducting film includes indium tin-oxide.
7. The electrode of claim 6, further comprising: an intermediate layer formed between the substrate and the buffer layer.
8. The electrode of claim 7, wherein the intermediate layer includes hydrophilic 3-aminopropyltriethoxysilane (APTES).
9. A flexible device comprising: a body; and a flexible, conductive, and transparent electrode formed on the body, wherein the electrode includes, a polymer based substrate, a polymer based buffer layer, wherein the polymer buffer layer includes a first polymer that is doped with a second polymer and further includes a polar solvent to increase its electrical conductivity, and a conducting film formed on the polymer based buffer layer, the conducting film being transparent to visible light.
10. The flexible device of claim 9, wherein the polymer based substrate is made of polyethylene terephthalate (PET).
11. The flexible device of claim 10, wherein the first polymer of the buffer layer is polymer poly-(3,4-ethylenedioxythiophene) (PEDOT), the second polymer of the buffer layer is poly-(styrenesulfonic acid) (PSS), the polar solvent is ethylene glycol (EG), and the conducting film includes indium tin-oxide.
12. The flexible device of claim 11, further comprising: an intermediate layer formed between the substrate and the buffer layer.
13. The flexible device of claim 12, wherein the intermediate layer includes hydrophilic 3-aminopropyltriethoxysilane (APTES).
14. The flexible device of claim 9, wherein the body is an optoelectronics device, a solar cell, a touch screen, a display, or a smart wearable device.
15. A method for making an electrode, the method comprising: providing a polymer based substrate; forming a polymer based buffer layer on the polymer based substrate, wherein the polymer buffer layer includes a first polymer that is doped with a second polymer and further includes a polar solvent to increase its electrical conductivity; and forming a conducting film, which is transparent to visible light, directly onto the polymer based buffer layer, wherein the electrode is flexible, electrically conductive and transparent to the visible light.
16. The method of claim 15, further comprising: forming an intermediate layer directly between the substrate and the buffer layer.
17. The method of claim 16, wherein the polymer based substrate is made of polyethylene terephthalate (PET), the first polymer of the buffer layer is polymer poly-(3,4-ethylenedioxythiophene) (PEDOT), the second polymer of the buffer layer is poly-(styrenesulfonic acid) (PSS), the polar solvent is ethylene glycol (EG), the conducting film includes indium tin-oxide, and the intermediate layer includes hydrophilic 3-aminopropyltriethoxysilane (APTES).
18. The method of claim 16, wherein the intermediate layer was made by molecular vapor deposition, the polymer based buffer layer was made by spin coating, and the conducting film was formed by sputtered deposition.
19. The method of claim 18, further comprising: vacuum annealing the electrode.
20. The method of claim 15, wherein the electrode is formed on an optoelectronics device, a solar cell, a touch screen, a display, or a smart wearable device.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate one or more embodiments and, together with the description, explain these embodiments. In the drawings:
[0013]
[0014]
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[0021]
DETAILED DESCRIPTION
[0022] The following description of the embodiments refers to the accompanying drawings. The same reference numbers in different drawings identify the same or similar elements. The following detailed description does not limit the invention. Instead, the scope of the invention is defined by the appended claims. The following embodiments are discussed, for simplicity, with regard to a flexible, transparent, and conductive electrode that can be used for optoelectronics. However, those skilled in the art would understand that this electrode can be used for other devices.
[0023] Reference throughout the specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with an embodiment is included in at least one embodiment of the subject matter disclosed. Thus, the appearance of the phrases “in one embodiment” or “in an embodiment” in various places throughout the specification is not necessarily referring to the same embodiment. Further, the particular features, structures or characteristics may be combined in any suitable manner in one or more embodiments.
[0024] According to an embodiment, a method for making ITO films with the ability to both flex and stretch (bending cycling and tensile strain) is now discussed. Such a method would have a large impact on the durability, performance and stability of transparent electrodes for the applications mentioned in the Background section.
[0025] According to this method, an organic material is used, in a synergetic way, with the ITO films, to further improve the properties of the ITO/substrate interface. For example, the present embodiment uses the polymer poly-(3,4-ethylenedioxythiophene) (PEDOT), doped with poly-(styrenesulfonic acid) (PSS), which serves as counter-ion for the positively charged PEDOT, to fabricate the ITO films on a given substrate. However, we note that PEDOT/PSS is here one application example among others and, possibly any type of conductive polymer can be used. The combination of PEDOT and PSS is called herein “PEDOT:PSS.” The PEDOT:PSS material has emerged as a good conductive polymer, due to its high conductivity and overall performance among other alternatives in aqueous form. [1], [2] Its conductive performance can be significantly improved by using solvents. Indeed, ethylene glycol or DMSO, for example, produces a rearrangement of the morphology of the films, thus promoting a phase separation between the conducting PEDOT and the insulating PSS. This leads to a better conducting network, and can even change the work function of the film. [3], [4], [5] Large increases in the PEDOT:PSS conductivity have been reported when using a polar solvent such as ethylene glycol (EG). [6]
[0026] Due to their inherent flexibility, conductive polymers are good candidates for flexible electronics. They can sustain higher strains and large numbers of bending cycles before being damaged. However, the polymers also show some important limitations. Their conductivities are usually lower than those of ITO-based solutions, and they suffer from a poor environmental stability. Due to its highly hygroscopic nature, PEDOT:PSS's behavior is temperature- and moisture-dependent, which results in degraded properties.
[0027] In one embodiment, the valuable properties of ITO (conductive, transparent, robust in harsh environment) have been merged with those of doped PEDOT:PSS (conductive, transparent, flexible). In this embodiment, a synergetic layered structure is obtained from the sputtered ITO film, together with an intermediate (or buffer) layer of EG-doped PEDOT:PSS on a Polyethylene terephthalate (PET) substrate for potential flexible optoelectronic applications. Using PET as the substrate (note that other substrates may also be used), the following structures have been generated: (1) ITO on PET (now onwards IP), (2) PEDOT:PSS on PET (now onwards PP), and (3) ITO on PEDOT:PSS on PET (now onwards IPP). Each of these structures has been tested for various parameters as discussed later.
[0028] For each one of the three structures noted above, the effects from annealing have also been quantified. The experiments performed by the inventors (their results are discussed later) demonstrate that the hybrid IPP layer, in which a very thin PEDOT:PSS buffer layer is introduced at the ITO/PET interface, possesses advantageous properties, somewhat “in-between” those of the IP and PP single-layer structures.
[0029] A method for making the IPP structure is now discussed with regard to
[0030] In step 102, one or more intermediate layers 204 (e.g., between zero and ten layers, each layer having a thickness of about 5 nm) of hydrophilic 3-aminopropyltriethoxysilane (APTES) is grown on the PET substrate 202. The intermediate APTES layer(s) may be deposited on the PET substrate 202 by using a molecular vapor deposition (MVD) technique. Note that other materials may be used to form layer 204 as long as these materials bond well to the films to be deposited later and/or to the substrate 202. The adsorption of the intermediate APTES layer 204 (likely through hydrogen bonding by the amine) to the polymer substrate 202 (PET in this case) helps the formation of lateral bonds which, in turn, help the formation of a multilayer via adhesion [7], [8]. Note that forming the intermediate layer 204 is optional.
[0031] Because of its simple structure and low cost, the MVD technique has been selected to deposit the intermediate hydrophilic layer of APTES. Those skilled in the art would understand that other techniques may be used for depositing the intermediate layer 204. However, if the MVD technique is used, an O.sub.2 plasma treatment is performed at 200 W, with an oxygen content of 200 sccm, for 100 sec (inside a MVD tool). To obtain a few intermediate layers of APTES (˜5 nm), the chamber pressure was kept at 4 mTorr and the temperature at 35° C. Again, these details of step 102 are provided for enablement and not for limiting the invention. Those skilled in the art could use other parameters and/or methods for achieving the same result.
[0032] Next, in step 104, a buffer layer 206 (e.g., PEDOT:PSS layer in this embodiment) is formed (see
[0033] In step 106, the ITO thin film 208 was formed over the buffer layer 206 as shown in
[0034] To obtain a high-quality ITO thin film 208 having a thickness of about 100 nm, the ITO material was deposited on the desired substrate at room temperature. Optimal deposition conditions were found to be at a sputtering power of 60 W, 3 mTorr sputtering pressure, 25 sccm of Argon gas flow, with a 7 cm-distance between the sample and the target, and with a substrate speed of rotation of 20 rpm. Those skilled in the art would understand that these conditions could be modified to still achieve the same results. Same of the deposited films were vacuum-annealed in step 108, at 150° C., for two hours.
[0035] The electrode 200 having the structure shown in
[0036] More specifically, as illustrated in
[0037] Various tests have been performed on the IP, PP and IPP structures discussed above. One of these tests determined the crystalline structure of the electrode. The crystalline structure (i.e., size and orientation of the grains) was determined by analysis of the X-ray diffraction (XRD) measurements, for the 2θ range of 10-55° (see
[0038] The specular optical transmittance for the various sets of samples in the wavelength range of 300-800 nm is shown in
[0039] Microscopic studies were also carried out to observe the surface morphology of the sputter-deposited ITO films on a typical PP structure. Scanning Electron Microscope (SEM) images of a typical sample of sputtered ITO thin film deposited on PEDOT:PSS on PET substrate has been taken at room temperature, and these images show a uniform distribution of grains, with an estimated size of 50 nm, comparable to the pattern obtained by XRD diffraction.
[0040] The electro-mechanical response of the strained thin films of the electrode 200 has also been investigated. In this study, the change in electrical resistance of the film when discrete degradations such as channel cracks and associated delamination are introduced were also studied. The experiment involved stretching the films in a tension mode to introduce a quasi-periodical pattern of cracks, and subsequently monitoring the change in electrical resistance as a function of the maximum applied strain, as well as a function of the crack density. The electrical resistance was first measured either after unloading the film (with a four-probe, as illustrated in
[0041] For the micro-tensile testing, the following conditions were observed. Straight rectangular samples (80 mm×10 mm) were obtained from films coated on 5″ PET substrates. The 4-point probe measurements were performed using Advanced Instrument technology (CMT Series), with a probe spacing of 1 mm. For 2-point probe measurements, linear electrodes (copper wires attached with Silver Paste) were placed on the coated side of the thin film samples. Electrodes were connected to an U2741A digital multimeter (Agilent Technologies) to measure changes in the electrical resistance, over a 30 mm gauge length, using a two-probe (in-situ) technique. All tests were performed in a controlled environment, with the temperature kept at 25° C. and relative humidity (RH) at 65% RH. The monotonic tensile tests were performed while monitoring the applied load (macroscopic strain) with a displacement rate of 1 mm/min, the crack density, as well as changes in the electrical resistance of the samples.
[0042] The tests were divided into multiple incremental loading/unloading cycles in order to have a maximum extension of 10%. After reaching a maximum extension for each cycle, the samples were partially unloaded to measure their post-cycling electrical resistance. All sets of thin film samples were tested to confirm the reproducibility of the experiments. Optical images were obtained for a region of interest located at the center of the specimen, using a microscope. Digital images were used to track the number of cracks during tests, and to evaluate the applied macroscopic strain. All in-situ microscopic images of various specimens were captured under controlled applied micro-tensile strain, using a specialized 1 kN Tensile Module.
[0043]
[0044] These results are explained as follows. At low strains, channel cracks run perpendicular to the loading direction and tend to form a quasi-periodical network with the increasing crack density. At higher strains, Poisson's effect induces transverse contraction, resulting in localized buckling and delamination. Previous studies have shown that the presence of delamination at a very early stage in the loading (due to a concentration of the stress at the crack tips) is the main responsible for the degradation of electrical performance. On the other hand, a hybrid performance was observed for as-deposited and annealed IPP layers (see
[0045] For the monotonic tensile loading, the in-situ electrical resistance was measured with respect to the applied strain and the results are shown in
[0046] From these tests, it was observed that the sheet resistance values for PEDOT-based films are higher than those for an ITO-based layered structure. When strain is applied, the sheet resistance for PEDOT-based films only shows nominal changes, whereas the sheet resistance for ITO films displays an increase by eight orders of magnitude, as soon as strain is applied. Thus, combining ITO with PEDOT in a composite layered structure results in a hybrid behavior characterized by high initial conductivity and high stability.
[0047] Next, the effect of channel crack density is discussed with regard to the novel IPP structure. The change in the electrical resistance in traditional layered structures is associated mainly with the multiplication of transverse cracks that trigger delamination between the conductive ITO and the substrate. For this reason, the dynamics of the multiplication of cracks in the IPP layered structure was investigated. For this investigation, in-situ SEM images were acquired during micro-tensile testing of an IPP stacked structure. Average strain values applied to the studied IPP structure were 1.67%, 3.33%, 6.67%, and 10%. The advantage of SEM images is that they offer very good contrast, which makes it possible to easily observe the characteristic features of the cracked pattern. The obtained images shown the multiplication of well-percolated channel cracks that give birth to secondary cracks, when the strain is significant. The multiplication of cracks, in-situ, was observed during the monotonic tensile tests presented above using optical microscopy. The corresponding digital images were used to both track the number of cracks during the test and evaluate the applied strain over the region of interest. To quantify the crack spacing with respect to the coating thickness, a dimensionless channel cracking rate ρ was defined, where ρ=h.sub.c/L, with h.sub.c being the coating layer thickness and L being the average inter-crack spacing, which is equal to the length of the region of interest (ROI) over which the cracks are counted and then divided by the number of cracks.
[0048] In summary, the first beneficial effect of the intermediate PEDOT/PSS layer is a reduction of the sensitivity of the electrical resistivity to the cracks as discussed with reference to
[0049] Next, environmental stability studies have been performed for the new IPP structure described with regard to
[0050] The above discussed embodiments disclose a new design based on a conductive polymer-assisted transparent and conducting ITO layer on a flexible substrate. Highly conductive and transparent sputtered ITO films on flexible PET substrates were prepared, either with or without an intermediate layer of PEDOT:PSS. They were then compared, in terms of their potentials for stretchable electrode-based applications and it was found that the brittle intrinsic nature of ITO layers makes them unsuitable for their use in flexible and stretchable devices. However, the as-deposited PEDOT:PSS layers are prone to the environmental degradation in atmosphere. The novel electrode 200 counterbalances the limitations of both materials as the tests show that, for a range of macroscopic strain values up to 30%, the hybrid structure features a low initial resistivity and a high stability, when subjected to mechanical strains. This can be attributed to an improvement of the electrical transfer at the delaminated interfaces, due to the presence of the conductive PEDOT/PSS layer. This PEDOT/PSS layer also has a beneficial effect on the degradation kinetics, as the channel cracking density tends to be lower in the hybrid structure, compared to the ITO-only structure. An explanation for this is the change in mechanical load transfer at the interface, due to the presence of this soft layer. It was also shown that, when different sets of samples (PP, IP and IPP layers, with and without maximum strain, and for both as-deposited and annealed samples) are exposed to a harsh environment (80% relative humidity, 50° C. temperature), the electrical sheet resistance dramatically increases for PP structures, whereas that of IP and IPP layered structures does not change significantly. The results presented herein show that an integration of the highly conductive ITO layers and the supporting conducting polymer layers of PEDOT:PSS films can be used as transparent electrodes in advanced stretchable and flexible devices.
[0051] The disclosed embodiments provide an electrode that is flexible, has high conductivity, and is transparent. It should be understood that this description is not intended to limit the invention. On the contrary, the exemplary embodiments are intended to cover alternatives, modifications and equivalents, which are included in the spirit and scope of the invention as defined by the appended claims. Further, in the detailed description of the exemplary embodiments, numerous specific details are set forth in order to provide a comprehensive understanding of the claimed invention. However, one skilled in the art would understand that various embodiments may be practiced without such specific details.
[0052] Although the features and elements of the present exemplary embodiments are described in the embodiments in particular combinations, each feature or element can be used alone without the other features and elements of the embodiments or in various combinations with or without other features and elements disclosed herein.
[0053] This written description uses examples of the subject matter disclosed to enable any person skilled in the art to practice the same, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the subject matter is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims.
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