Patent Description:
Therefore, the present invention could be included in the field of paper-based green electronics.

In recent years, studies have been intensely made to develop organic and flexible diodes in which polymeric functional materials and temperature sensitive substrates such as plastic foils are employed.

As a matter of definition herein, a diode is a semiconductor device characterized by a rectifying interface which blocks or allows the current through it depending on the applied bias. It can be fabricated using broad architectures and organic materials processed from solution. Typical diode architectures are based on P-N or Schottky junctions where p-type/n-type organic semiconductor (OSC) or metal/OSC are the rectifying interfaces, respectively. P-N junctions require the use of two kinds of semiconductors with different type of majority charge carriers and to align the electrodes Work Function (WF) to the P-N semiconductor WF to obtain the formation of ohmic contacts. It should be further noted that the inherent diffusion of the majority charge carriers provokes a built-in potential of typically <NUM>. 7eV, thereby the devices start to operate above this potential.

the implementation of inkjet organic diodes based on P-N junctions is still challenging. A more commonly employed architecture for the fabrication of organic diodes is the Schottky junction, which is based on ohmic electrode/OSC/rectifying electrode stack. Nevertheless, it is known that this structure presents challenges since the rectifying interface results from the contact between the OSC and specific WF electrodes. The two electrodes are chosen according to the alignment between their WFs and the OSC energy levels. One of the electrodes WFs must be aligned with the OSC WF to obtain an ohmic contact, whereas the other must be misaligned to obtain a rectifying interface. This limitation affects the natural progress of these devices in the field of organic electronics.

The development of solution-based electronic components offers the possibility to manufacture flexible and lightweight electronics using additive processes. Inkjet printing, in particular, has been receiving growing interest as a method for the deposition of functional materials, as opposed to more conventional approaches. Although this technique has been widely used for the fabrication of flexible organic devices, so far, a simple diode still remains a challenge for the technology.

To date, the related art has failed to effectively fabricate an organic Schottky diode using polymeric materials by means of inkjet printing onto temperature sensitive substrates. The low availability of solution-based metals with uneven WFs required to obtain a rectifier interface, hampers the implementation of diodes into large area manufacturing such as additive fabrication techniques. Although few metallic inks are commercially available and feature these characteristics, these materials often need the application of aggressive post-treatments, such as intense pulsed light (IPL) sintering or high curing temperatures among others, making them incompatible with OSCs and temperature sensitive substrates, as plastic or cellulose substrates. Evaporation and sputtering are still the most common techniques for the deposition of metal electrodes in the fabrication of organic diodes.

Accordingly, <NPL> describes a diode susceptible of being processed by inkjet printing additive manufacturing comprising printing a first layer onto the conductive substrate by means of an additive, drop casting of a second layer onto the cured product obtained before and drop casting of a third layer onto the cured product further obtained before. <NPL> describes a conductive substrate comprising a conductive nanopaper with cellulose nanofibers in a weight percent of <NUM> wt% and a conductive material ("PPy") in a weight percent of <NUM> wt% with respect to the total weight of the conductive substrate, said conductive material being a conductive polymer.

All these requirements make difficult a rapid implementation of organic diodes into real applications; therefore, it would be advantageous to overcome these limitations. Another aspect that has to be taken into account is that, in semiconductor devices, especially flexible organic diodes, a substantial portion of non-biodegradable solid waste is represented by plastic substrates.

Thus, it is needed to develop novel diodes that are able to face and overcome all the issues presented so far.

The invention refers to a flexible and lightweight diode, which can be included within the term paper-based green electronics. The diode of the present invention is based on a conductive nanopaper being therefore a sustainable, biodegradable and eco-friendly electronic component. In the diode of the present invention the conductive nanopaper is acting as both, substrate and cathode.

The first aspect of the present invention refers to a diode (herein "the diode of the present invention") susceptible of being processed by inkjet printing additive manufacturing characterized in that it comprises:.

and wherein the conductive substrate is acting as cathode and the third layer is acting as the anode.

The diode of the present invention is characterized by a high mechanical response, with a tensile strength of about <NUM> MPa and Young's modulus of about <NUM> GPa; and it is flexible, which means that the substrate is foldable in around <NUM> degrees and the organic semiconductor can maintain its properties under a strain of up to <NUM>%.

The diode of the present invention is lightweight, this means that its density is kept below <NUM> cm-<NUM>.

In the present invention the conductive nanopaper is acting as conductive substrate and as cathode, forming an ohmic contact with the first layer comprising a polymeric insulator.

The substrate of the present invention is a conductive substrate which, at the same time, holds the devices and acts as cathode, becoming an active component of the diode. This is possible thanks to the fact that the rectifying characteristic arises from the first layer of a polymeric insulator/second layer of organic p-type semiconductor interface (insulator/OSC interface), releasing the cathode from being responsible of the rectification.

The conductive substrate of the diode of the present invention is a conductive nanopaper comprising:.

In a preferred embodiment of the diode of the present invention the conductive substrate consists of a conductive nanopaper, said conductive nanopaper consists of:.

wherein the sum of the percentages by weight is <NUM> wt%.

The proposed invention allows to skip the deposition of the cathode onto non-functional substrates and of an eventual additional planarization layer on the substrate, allowing a reduction in material, time, and cost consumption.

In a preferred embodiment of the diode of the present invention, the conductive polymer of the conductive substrate is selected from poly(<NUM>,<NUM>-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and polypyrrole (PPy).

The first layer of the diode of the present invention comprises a polymeric insulator which is an ink comprising amorphous silica, epoxy resin and epoxy hardener.

The second layer of the diode of the present invention comprises an organic p-type semiconductor (OSC). Preferably, the organic p-type semiconductor (OSC) of the second layer is poly(triaryl amine) (PTAA).

The third layer of the diode of the present invention is acting as anode.

In a preferred embodiment of the diode of the present invention, the third layer is a metal layer, wherein the metal is selected from Ag and Au.

In another preferred embodiment of the diode of the present invention the third layer is a polymeric layer of poly(<NUM>,<NUM>-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS).

As mentioned before, the interface between the first layer comprising a polymeric insulator and the second layer comprising an organic p-type semiconductor (insulator/OSC interface) is responsible for the rectifying characteristics of the diode of the present invention. The asymmetric characteristic of a diode is typically related to a change in its resistance, which is negligible in forward bias and high in reverse bias condition. OSCs usually favor only one type of carrier depending on the ease with which holes or electrons can be injected into said OSC from the electrodes.

Two different regimes of operation can be distinguished in the diode of the present invention: accumulation and depletion, defined according to the effect that the applied voltage has on the p-type OSC.

Under the application of a positive voltage to the hole transport p-type OSC semiconductor, free charges are injected and accumulated at the insulator/OSC interface (accumulation region). If a high conductance is registered across the insulator, the accumulation capacitance does not saturate, and a certain amount of current can pass through the insulator (forward bias).

Conversely, when a negative bias is applied to the organic p-type semiconductor (OSC), charges accumulate at the third layer (anode) electrode/ organic p-type semiconductor (OSC) interface. Thus, there is no charge at the polymeric insulator/ organic p-type semiconductor (OSC) interface, leaving only a space charge or depletion layer (reverse bias). The reverse leakage current and forward current give indications about the depletion region and accumulation region at the interface between the organic p-type semiconductor (OSC) and the polymeric insulator.

Therefore, one of the multiple advantages of the present diode is that the work function (WF) of the organic p-type semiconductor (OSC) and the polymeric insulator do not need to be aligned. The main requirement for the diode of the present invention comes from the leakage behaviour of the polymeric insulator. The polymeric insulator must be leaky enough to allow the current flow in forward bias, without leading to short-circuits. Since the majority of the organic p-type semiconductors (OSCs) present similar WFs compared to the ones of metallic inks, the formation of an ohmic contact at the OSC/electrode interface is totally feasible.

As stated before, the current flows through the diode of the present invention thanks to the presence of a leaky insulator. As it is known, the roughness of an underneath layer affects the quality and performance of the subsequent one. Based on that, conductive cellulose-based substrates are preferable candidates thanks to their higher roughnesses compared to common polymeric substrates. Whereas inkjet printed conductive electrodes (cathodes) onto the non-functional cellulose substrate would reduce the intrinsic and beneficial roughness of the cellulose, a substrate comprising a conductive polymer and cellulose nanofibers preserves the roughness needed to perturbate the good performance of the insulator. This feature is paramount to highlight because up to date rough substrates were detrimental for the correct operation of electronic devices.

In another preferred embodiment of the diode of the invention said diode is a diode-logic gate. Diode logic (DL) technology is the use of diodes to build Boolean logic gates. The most common application for DL is in Diode-Transistor Logic (DTL) integrated circuits. Diodes can perform switching and digital logic operations. Forward and reverse bias switch a diode between the low and high impedance states, respectively. So that it may serve as a switch. Logic Diodes can perform digital logic functions: "AND" and "OR".

The present invention also refers to the process for the manufacturing of the diode of the present invention (herein "the process of the invention") by inkjet printing additive manufacturing technique in which organic materials and nanoparticle-based materials are allowed in the form of solution. Said process comprises a step of printing the first layer comprising a polymeric insulator onto the conductive substrate comprising conductive nanopaper by means of an additive manufacturing technique, preferably by means of inkjet printing additive manufacturing technique.

Therefore, a second aspect of the present invention refers to a process for the manufacturing of a diode of the present invention described above, characterized in that it comprises the following steps:.

In a preferred embodiment of the process of the invention the conductive substrate of step (a) is obtained by following the next steps:.

The last aspect of the present invention refers to an electronic component comprising the diode of the present invention described above. Therefore, the present diode of the invention can be part of integrated circuits or electronic systems as discrete device. Diodes along with other electronic components such as resistors, transistors, etc. can create electronic circuits with a particular function, as for example rectifiers, oscillators, among others.

<FIG> shows a vertical section of the diodes of the present invention. The diodes are fabricated on a nanopaper of Cellulose NanoFibers (CNF) doped with a conductive polymer, as, for example, PEDOT:PSS. This component acts as both the substrate (<NUM>) and the bottom electrode-cathode of the diode.

The first layer (<NUM>) is a polymeric insulator (amorphous silica, epoxy resin, or crosslinked polyvinylphenol) inkjet-printed onto the conductive nanopaper.

The second layer (<NUM>) is of organic p-type semiconductor (OSC), as, for example, the amorphous OSC such as PTAA.

The third layer (<NUM>) is the second electrode-anode.

<FIG> shows an optical image of the diode. The numeration of the layers is the same as the one adopted in <FIG>.

<FIG> shows the fabrication scheme of the diodes of the present invention.

The first component of the diode to be fabricated is the conductive nanopaper that acts as both the substrate (<NUM>) and the bottom electrode-cathode.

The preparation of cellulose nanofibers follows the TEMPO-mediated oxidation at basic pH described in with <NUM> mmol of NaClO until constant pH of <NUM>. After TEMPO-oxidation, the cellulose suspension is filtered and washed five times with distilled water to remove all non-reacted reagents and free ions. After that, the cellulose suspension at about <NUM> wt% concentration is passed through a high-pressure homogenizer (NS1001L PANDA PLUS 2K_GEA), <NUM> times at each pressure of <NUM>, <NUM> and <NUM> bars.

For the preparation of the conductive nanopaper, the cellulose nanofiber is diluted to about <NUM> wt% concentration with distilled water, dispersed for <NUM> by means of an ultra-turrax (IKA, GmbH& Co. KG, Germany) and sonicated, for <NUM> at an amplitude of <NUM>% in two equal intervals with a <NUM> standby, using a Q700 sonicator.

For the fabrication of conductive nanopapers with PEDOT:PSS as the conductive polymer, the conductive polymer is also diluted with distilled water to about <NUM> wt% and stirred for <NUM>. The PEDOT:PSS suspensions is then added into the above CNF suspension with different proportions of CNF-PEDOT:PSS (<NUM>/<NUM> and <NUM>/<NUM>). The mixture is stirred for <NUM>, filtered with a vacuum filter, and dried for <NUM> at <NUM> under a pressure of <NUM> - <NUM> bar using a Rapid Köthen sheet dryer.

The first layer (<NUM>) of the diode is inkjet printed using a Fujifilm Dimatix DMP2831 desktop inkjet printer. As polymeric insulator of the first layer (<NUM>) amorphous silica, epoxy resin, and crosslinked polyvinylphenol has been tested. Polymeric insulator of the first layer (<NUM>) is printed onto the conductive nanopaper. Different curing steps can be adopted according to the chosen polymeric insulator (<NUM>).

The third layer (<NUM>) is an organic p-type semiconductor like the amorphous the organic p-type semiconductor poly(triaryl amine) (PTAA), is deposited on the top of the polymeric insulator of the first layer (<NUM>) using drop casting (<NUM>µL). The curing process is performed on a hot plate for <NUM> minutes at <NUM>. The second electrode-anode is the third layer (<NUM>), for example, a silver conductive paste deposited by means of drop casting and dried in air.

<FIG> shows an optical image (i) and a SEM (image (ii) of the diode. The numeration of the layers is the same as the one adopted in <FIG>.

<FIG> shows the electrical characterization of the diode. <FIG> shows the typical rectifying behavior of the presented diode. The rectifier barrier is located at the insulator/semiconductor interface.

The Rectification Ratio (RR) is defined as the ratio of the maximum forward bias current to the maximum reverse bias current at the same voltage. The diode reported in <FIG> presents a RR of <NUM>.

Claim 1:
A diode that comprises:
• a conductive substrate (<NUM>) wherein the thickness of said conductive substrate (<NUM>) is ranging between <NUM> and <NUM>,
• a first layer (<NUM>) comprising a polymeric insulator located on the substrate (<NUM>),
wherein the thickness of said first layer (<NUM>) is ranging between <NUM> and <NUM>,
• a second layer (<NUM>) comprising an organic p-type semiconductor located on the first layer (<NUM>),
• a third layer (<NUM>) located on the second layer (<NUM>),
• wherein the conductive substrate (<NUM>) is acting as cathode and the third layer (<NUM>) is acting as anode,
characterized in that:
• the conductive substrate comprises a conductive nanopaper, said conductive nanopaper comprising:
∘ cellulose nanofibers in a weight percent of between <NUM> wt% and <NUM> wt% with respect to the total weight of the conductive substrate (<NUM>), and
∘ a conductive material in a weight percent of between <NUM> wt% and <NUM> wt% with respect to the total weight of the conductive substrate (<NUM>), said conductive material selected from a conductive polymer, carbon nanotubes or a combination thereof,
• the thickness of said second layer (<NUM>) is ranging between <NUM> and <NUM>,
• the thickness of said third layer (<NUM>) is ranging between <NUM> and <NUM>, and the polymeric insulator of the first layer (<NUM>) is a cured ink comprising amorphous silica, epoxy resin and epoxy hardener.