A UV-degradable transient electronic device and preparation method thereof

Abstract

The present invention discloses an ultraviolet-light-degradable transient electronic device and a preparation method thereof. Using a polymer cPPA transient thin film as an intermediate layer, the corresponding transient electronic device is fabricated. Under ultraviolet light irradiation, it achieves controllable degradation: The transient resistor uses the transient thin film as the substrate of the device, which is beneficial to the stable operation of the device under normal conditions. During the degradation process, the substrate fails, resulting in the rapid failure of the resistor function and physical degradation. Utilizing the N-type characteristic of the polymer cPPA transient thin film, it forms the main structure PN junction of the diode with the semiconductor oxide ZnO, thereby realizing the unidirectional conductivity of the diode. It also uses the polymer cPPA transient thin film and the high-k oxide Yi2O3 to form a high-k dielectric layer, forming a high-k capacitor with excellent capacitance performance. It can be controllably degraded under ultraviolet light, and can be rapidly and controllably degraded while having excellent electrical properties.

Description

Technical Field

[0001] The invention relates to the technical field of electronic devices, and in particular to an ultraviolet light-degradable transient electronic device and a preparation method thereof. Background Art

[0002] The rapid development of electronic devices has provided a lot of convenience for people's lives. In the past few decades, it has always been the goal of researchers to develop electronic devices with excellent performance and strong durability. Therefore, the substrate materials and electronic materials used in electronic devices are stable and not easy to degrade. At the same time, the toxic electronic waste of electronic devices has also caused certain pollution to the environment. With the expansion of the use of electronic devices, damaged or obsolete electronic devices are abandoned everywhere all the time. Under natural conditions, the discarded electronic devices cannot be naturally degraded, which has brought serious environmental pollution and has developed into one of the important problems threatening human social life.

[0003] In the existing technology, "transient electronics" is an important method to solve this problem and is also a hot area of ​​current research. Transient electronics maintain high performance and stability in the studio, and can achieve the degradation of electronic devices in a relatively short time when needed. At present, it plays an important role in information security, biomedicine, environmental sensors, etc. Compared with traditional electronic devices, transient electronic devices can achieve the disappearance of physical form and device function under the regulation of external stimuli or related instructions. However, the transient materials and their applications in the existing technology are still in the early stages, their controllable conditions are harsh, and the material properties are unstable. How to apply them has further restricted the development of transient electronic devices. Summary of the invention

[0004] In view of the above-mentioned deficiencies in the prior art, an object of the present invention is to provide a transient electronic device that can be degraded by ultraviolet light, so as to solve the problem that the degradation conditions of transient electronic devices in the prior art are harsh and difficult to control.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] A UV-degradable transient electronic device is characterized in that a polymer cPPA transient film is used as an intermediate layer, and a metal component is arranged on the polymer cPPA transient film to obtain the UV-degradable transient electronic device.

[0007] Furthermore, when the transient electronic device is a transient resistor, the structure of the transient resistor is that the polymer cPPA transient film is used as a substrate, and Mg metal material is deposited on the surface of the substrate.

[0008] When the transient electronic device is a transient diode, the structure of the transient diode is that an ITO glass sheet is used as a substrate and a bottom electrode, a polymer cPPA transient film is attached to the resistance surface of the substrate, a ZnO layer is deposited on the surface of the polymer cPPA transient film, and Cu is provided on the surface of the ZnO layer as a top electrode.

[0009] When the transient electronic device is a transient capacitor, the structure of the capacitor is that ITO glass is used as the substrate and the bottom electrode, a polymer CPPA transient film is attached to the surface of the substrate, and Yi 2 O 3 The dielectric layer has a Cu top electrode disposed on the surface of the dielectric layer.

[0010] The present invention also provides a method for preparing a UV-degradable transient electronic device, comprising the following steps: laminating a mask plate on the surface of a polyphthalaldehyde film, depositing Mg metal on the surface of the polyphthalaldehyde film, and removing the mask plate to obtain a transient resistor device.

[0011] Furthermore, an ITO glass sheet is selected as a substrate and a bottom electrode, the ITO glass sheet is cleaned and then dried with nitrogen, a polyphthalaldehyde film is attached to a surface of the ITO glass sheet on which a resistor is provided, after pressing for a period of time, a mask plate is attached to the surface of the polyphthalaldehyde film, a ZnO target material is deposited on the surface of the polyphthalaldehyde film, a lattice mask plate is attached to the ZnO layer, and a Cu target material is sputtered onto the ZnO layer to form a lattice top electrode, thereby obtaining a transient diode.

[0012] Furthermore, ITO glass was used as the substrate and bottom electrode of the capacitor, and a polyphthalaldehyde film was attached to the surface of the ITO glass. 2 O 3 Sputtered onto the surface of polyphthalaldehyde film, and then 2 O 3 A Cu top electrode is sputtered on the layer to obtain a transient capacitor.

[0013] Compared with the prior art, the present invention has the following beneficial effects:

[0014] 1. The present invention uses polymer cPPA transient film as an intermediate layer to prepare corresponding transient electronic devices, which achieve controllable degradation under ultraviolet light irradiation: the transient resistor uses the transient film as the substrate of the device, which is conducive to the stable operation of the device under normal circumstances. During the degradation process, the substrate fails, resulting in rapid failure of the resistor function and physical degradation.

[0015] 2. The present invention utilizes the N-type property of the polymer cPPA transient film to form the main structure PN junction of the diode with the semiconductor oxide ZnO, thereby realizing the unidirectional conductivity of the diode. 2 O 3 A high-k value dielectric layer is formed to form a high-k value capacitor with excellent capacitance performance.

[0016] 3. The method for preparing ultraviolet light-degradable transient electronic devices provided by the present invention has the characteristics of simple process and controllability. The obtained electronic products can be controllably degraded under ultraviolet light and can be rapidly and controllably degraded while having excellent electrical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a schematic structural diagram of the ultraviolet light degradable transient resistor of the present invention.

[0018] Figure 2 The resistance value of the resistor changes with and without ultraviolet radiation. 1 is the resistance value change with ultraviolet radiation; 2 is the resistance value change without ultraviolet radiation.

[0019] Figure 3 Figure 2 shows the degradation process of the resistor: (a) not irradiated; (b) irradiated with UV light for 40 min; (c) left standing for 4 h after irradiation; (d) left standing for 14 h after irradiation.

[0020] Figure 4 This is the structure diagram of the light radiation transient diode.

[0021] Figure 5 This is the volt-ampere characteristic curve of the diode.

[0022] Figure 6 This is the volt-ampere characteristic curve after testing 10 times.

[0023] Figure 7 The diode photolysis state diagram: (a) the state when no ultraviolet light is irradiated; (b) the state when ultraviolet light is irradiated for 10 minutes; (c) the state when ultraviolet light is irradiated for 20 minutes; (d) the state when ultraviolet light is irradiated for 30 minutes; (e) the state when ultraviolet light is irradiated for 40 minutes; (f) the state when ultraviolet light is irradiated for 1 hour.

[0024] Figure 8 This is the structural diagram of the light radiation transient capacitor.

[0025] Fig. 9 is the capacitance value of the transient capacitor at different frequencies.

[0026] Fig.10 is the 2 minute capacitance value of the transient capacitor. DETAILED DESCRIPTION

[0027] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

[0028] 1. Polymer cPPA transient film used in the present invention

[0029] 1. A method for preparing a UV-degradable polymer material, comprising the following steps:

[0030] (1) adding o-phthalaldehyde into a reactor and making the reactor reach a vacuum state, filling the reactor with nitrogen, and then adding anhydrous dichloromethane into the reactor; wherein the concentration of o-phthalaldehyde in the anhydrous dichloromethane is 0.01 g / mL to 0.3 g / mL;

[0031] (2) stirring the solution in the reactor and cooling it to below -78°C, and adding boron trifluoride ether to the reactor; wherein the content of boron trifluoride ether in the solution in the reactor is 0.005 g / mL to 0.02 g / mL;

[0032] (3) After the solution in the reactor is stirred for 1h~2h, pyridine is added and the solution in the reactor is stirred for 1h~2h. Then the reactor is placed at room temperature and the mixture in the reactor is poured into Methanol A white flocculent precipitate is formed in the reactor; wherein the concentration of pyridine in the solution in the reactor is 0.02 g / mL~0.08 g / mL.

[0033] (4) Dissolve the white flocculent precipitate obtained in step (3) in Anhydrous dichloromethane The mixed solution is poured into Methanol The product is re-precipitated and further purified to obtain a white block fiber; the fiber is dried to volatilize the methanol therein to obtain a UV-degradable polymer material polyphthalaldehyde cPPA.

[0034] 2. Using the above polymer material polyphthalaldehyde to prepare a cPPA transient film, comprising the following steps:

[0035] Adding a polymer material polyphthalaldehyde cPPA, a photoacid generator MBTT, a curing agent DGD and an organic solvent dioxane into a light-proof sample bottle, and stirring them evenly to obtain a reaction solution, transferring the reaction solution into a container, and subjecting it to a negative pressure constant temperature treatment to obtain a smooth and complete cPPA transient film;

[0036] In the reaction solution, the concentration of polyphthalaldehyde is 0.05 g / mL to 0.3 g / mL; the concentration of the photoacid generator MBTT is 3 mg / mL to 10 mg / mL; the concentration of the curing agent diethylene glycol dibenzoate is 0.1 mg / mL to 0.3 mg / mL; and the balance is the organic solvent dioxane.

[0037] The photoacid generator MBTT is 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine; the curing agent DGD is diethylene glycol dibenzoate; the solvent dioxane is 1,4-dioxane, the molecular formula of which is C 4 H 8 O 2 .

[0038] Second, a polymer cPPA transient film is used as an intermediate layer, and a metal component is arranged on the polymer cPPA transient film to obtain a UV-degradable transient electronic device.

[0039] 1. Optical Radiation Transient Resistor

[0040] like Figure 1 As shown, when the transient electronic device is a transient resistor, the structure of the transient resistor is to use a polymer cPPA transient film as a substrate, and deposit Mg metal material on the surface of the substrate. The transient resistor is prepared by the following method: attaching a mask plate to the surface of a polyphthalaldehyde film, depositing Mg metal on the surface of the polyphthalaldehyde film, and removing the mask plate to obtain the transient resistor.

[0041] Since the light radiation degradable film will produce hydrochloric acid under ultraviolet light, and hydrochloric acid will produce an acidic environment, which can dissolve many active metal electrodes. Therefore, a degradable resistor with Mg as the metal material and light radiation transient film as the substrate is designed. The resistor maintains its resistance performance under non-triggering conditions, and degrades itself under ultraviolet light conditions. The specific preparation process of the resistor is: attach the mask to the surface of the light radiation transient film, deposit Mg metal on the surface of the light radiation transient film through physical vapor deposition technology, and remove the mask to complete the preparation of the resistor.

[0042] Connect the light radiation transient resistor to a 2700 digital multimeter and test the resistance of the resistor. Under non-trigger conditions, the resistance value of the resistor is stable at around 24 Ω, and under ultraviolet radiation, the resistance value increases slowly in the first 40 minutes, and then rises sharply at 40 minutes, and the path of the resistor becomes open. The self-destruction function of the light radiation transient resistor is verified. The resistance value change curve of the resistor with and without ultraviolet radiation is shown in the figure below. Figure 2 shown.

[0043] As time goes by, under the condition of ultraviolet light, the polymer substrate film begins to degrade acidically, and the metal on the surface of the resistor will also dissolve in the acidic substance, so the resistance of the resistor will increase. After 1 hour of ultraviolet light irradiation, the resistance of the resistor increases significantly. After 1.5 hours of ultraviolet light irradiation, the resistor is completely degraded. Figure 3 shown.

[0044] Analysis of the principle of degradable resistors: Under ultraviolet light, the photoacid generator in the degradable film will combine with H in the air to produce HCl. Metal materials can react with hydrochloric acid and the reaction is relatively violent. However, magnesium is relatively active and is easy to react with air to generate magnesium oxide and wrap on the surface of metal magnesium. Although magnesium oxide does not react as violently with hydrochloric acid, it is also easy to react with hydrochloric acid. The specific reaction equation is:

[0045]

[0046] 2. Optical Radiation Transient Diode

[0047] like Figure 4 As shown, when the transient electronic device is a transient diode, the structure of the transient diode is to use an ITO glass sheet as a substrate and a bottom electrode, a polymer cPPA transient film is attached to the resistance surface of the substrate, a ZnO layer is deposited on the surface of the polymer cPPA transient film, and Cu is provided on the surface of the ZnO layer as a top electrode.

[0048] The diode has unidirectional conductivity and has a significant rectifying effect. When a forward voltage (exceeding the cut-off voltage) is applied, the diode is turned on, and when a negative voltage is applied, the diode is in the cut-off state. Transient metal oxide ZnO is selected as a P-type semiconductor, and the PN junction of the transient diode is formed with a degradable transient film with a smooth surface and uniform dielectric distribution.

[0049] The preparation process of the optical radiation transient diode is as follows:

[0050] Select an ITO glass sheet of a certain specification as the substrate and bottom electrode. Pretreat the ITO glass. Ultrasonic clean it with acetone, anhydrous ethanol and deionized water for 20 minutes respectively, and then dry the glass sheet with nitrogen. Cut the transient film into squares and flatly bond the transient film to the ITO film (with the resistor surface). Press it with a 100 g weight for 10 minutes. Ensure the integrity of the interface. Bond the mask to the surface of the transient film, and use the magnetron sputtering process to deposit the ZnO target on the surface of the transient film. Bond the lattice mask to the ZnO layer, and sputter the Cu target to the ZnO layer to form a lattice top electrode.

[0051] The volt-ampere characteristic curve of the diode can be measured by contacting the ITO bottom electrode and the Cu top electrode to form a circuit. The volt-ampere characteristic curve of the diode is as follows: Figure 5 shown.

[0052] It can be found that the diode has an obvious rectification effect. Its forward threshold voltage is about 1.5V. At a forward voltage of 2.5V, the conduction voltage is 2.0*10-10A. Repeatability test of transient diodes, apply -1V to 8V voltage to the diode, observe the diode's volt-ampere characteristic curve, repeat the test 10 times and the volt-ampere characteristic curve is as follows: Figure 6 shown.

[0053] The transient diode was placed under ultraviolet light triggering conditions to observe the photodegradation performance of the diode. After 10 minutes of ultraviolet light irradiation, a small amount of oily substance was produced on the surface of the film. After 20 minutes of ultraviolet light irradiation, a small part of the Cu electrode on the surface of the film dissolved, and the entire film substrate began to curl up. After 30 minutes of ultraviolet light irradiation, cracks appeared in the middle of the film, and a large amount of oily substance appeared around it. After 40 minutes of ultraviolet light irradiation, the film degraded into two parts with only a small part of the dot electrode remaining on the film surface. After 1 hour of ultraviolet light irradiation, the film completely turned into a pool of oily substance, and the dot matrix electrode on the surface had completely dissolved. The diode photodecomposition state diagram is shown in the figure Figure 7 shown.

[0054] The principle of the light radiation transient diode: The core of the diode is the PN junction composed of the ZnO thin film layer (P-type) and the degradable transient thin film layer (N-type).

[0055] 3. Light Radiation Transient Capacitor

[0056] like Figure 8 As shown, when the transient electronic device is a transient capacitor, the structure of the capacitor is that ITO glass is used as a substrate and a bottom electrode, a polymer cPPA transient film is attached to the surface of the substrate, and Yi 2 O 3 The dielectric layer has a Cu top electrode disposed on the surface of the dielectric layer.

[0057] The capacitor structure is prepared by using a metal-insulator-metal structure, with ITO glass as the substrate and bottom electrode of the capacitor. The polymer cPPA transient film is attached to the ITO surface, and then the high-k oxide Yi is deposited by magnetron sputtering. 2 O 3 Sputtering onto the surface of the polymer transient film. Then, a copper top electrode layer is evaporated on the dielectric layer, and the polymer cPPA transient film is completely prepared. The transient capacitance is tested using an impedance tester, such as Fig. 9 and Fig.10As shown, the capacitance value of the transient capacitor at different frequencies is around 22 pF, indicating that the transient capacitor can carry a large amount of charge. It can also be seen that the capacitance stability of the capacitor within a certain period of time is relatively good.

[0058] The present invention uses polymer cPPA transient film as an intermediate layer to prepare corresponding transient electronic devices, which can achieve controllable degradation under ultraviolet light irradiation: the transient resistor uses the transient film as the substrate of the device, which is conducive to the stable operation of the device under normal conditions. During the degradation process, the substrate fails, resulting in rapid failure of the resistor function and physical degradation. The polymer cPPA transient film is N-type, and forms the main structural PN junction of the diode with the semiconductor oxide ZnO, thereby achieving unidirectional conductivity of the diode. The polymer cPPA transient film is also used with the high-k oxide Yi 2 O 3 A high-k value dielectric layer is formed to form a high-k value capacitor with excellent capacitance performance.

[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the technical solution. Those skilled in the art should understand that those modifications or equivalent substitutions of the technical solution of the present invention that do not depart from the purpose and scope of the technical solution should be included in the scope of the claims of the present invention.

Claims

1. A UV-degradable transient electronic device, It is characterized in that A polymer cPPA transient film is used as an intermediate layer, and a metal component is arranged on the polymer cPPA transient film to obtain a UV-degradable transient electronic device; wherein the transient film contains a photoacid generator MBTT, and the transient electronic device is a transient diode or a transient capacitor.

2. The UV-degradable transient electronic device according to claim 1, It is characterized in that When the transient electronic device is a transient diode, the structure of the transient diode is that an ITO glass sheet is used as a substrate and a bottom electrode, a polymer cPPA transient film is attached to the resistance surface of the substrate, a ZnO layer is deposited on the surface of the polymer cPPA transient film, and Cu is provided on the surface of the ZnO layer as a top electrode.

3. The UV-degradable transient electronic device according to claim 1, It is characterized in that When the transient electronic device is a transient capacitor, the structure of the capacitor is that ITO glass is used as the substrate and the bottom electrode, a polymer CPPA transient film is attached to the surface of the substrate, and Yi 2 O 3 The dielectric layer has a Cu top electrode disposed on the surface of the dielectric layer.

4. A method for preparing a UV-degradable transient electronic device, It is characterized in that The method comprises the following steps: selecting an ITO glass sheet as a substrate and a bottom electrode, cleaning the ITO glass sheet and then drying it with nitrogen, laminating a polyphthalaldehyde film to a surface of the ITO glass sheet on one side of which a resistor is provided, pressing for a period of time, laminating a mask plate to the surface of the polyphthalaldehyde film, depositing a ZnO target material on the surface of the polyphthalaldehyde film, laminating a lattice-shaped mask plate to the ZnO layer, sputtering a Cu target material to the ZnO layer, forming a lattice-shaped top electrode, and obtaining the transient diode as claimed in claim 2.

5. A method for preparing a UV-degradable transient electronic device, It is characterized in that The steps include: using ITO glass as the substrate and bottom electrode of the capacitor, laminating the polyphthalaldehyde film on the surface of the ITO glass, 2 O 3 Sputtered onto the surface of polyphthalaldehyde film, and then 2 O 3 A Cu top electrode is sputtered on the layer to obtain the transient capacitor as claimed in claim 3.

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