CN114665004A - Multifunctional diode piezoelectric sensor, preparation method and wearable device - Google Patents
Multifunctional diode piezoelectric sensor, preparation method and wearable device Download PDFInfo
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Abstract
The embodiment of the invention provides a multifunctional diode piezoelectric sensor, a preparation method and wearing equipment, wherein the preparation method comprises the following steps: the device comprises a flexible substrate, a metal top electrode and a metal oxide conductive bottom electrode, wherein the metal top electrode and the metal oxide conductive bottom electrode are manufactured on the flexible substrate; the multifunctional diode piezoelectric sensor is provided with a P-N junction diode structure, and the P-N junction diode structure is positioned between a metal top electrode and a metal oxide conductive bottom electrode; the N-type layer of the P-N junction diode structure is arranged below the P-type layer of the P-N junction diode structure; the N-type layer of the P-N junction diode structure is made of semiconductor piezoelectric materials, and the P-type layer of the P-N junction diode structure is made of organic semiconductors; and a PET passivation layer is packaged on the upper surface of the P type layer. The piezoelectric performance is good, the sensitivity is high in a detection mode, and the detection range is wide; the energy can be collected while detecting, and an external power supply is not needed.
Description
Technical Field
The invention relates to the field of flexible electronics, in particular to a multifunctional diode piezoelectric sensor, a preparation method and wearing equipment.
Background
Flexible electronics has received much attention as a broad scientific field, especially when it is targeted to wearable devices, energy harvesters and tactile sensors. In such situations, several challenges have been addressed, but several difficulties remain to be overcome. Despite the rapid technological advances, both tactile sensing and energy harvesting have not achieved a good combination. In fact, the devices reported in the present state of the art with respect to energy harvesters or tactile sensors are considered to be two distinct devices operating in distinct modes, and combining the two into one device is a technical difficulty. Energy harvesting techniques, particularly the widely used piezoelectric material energy harvesters, actually require the storage of regulated voltage signals in a specific power management circuit board. In this case, it is cumbersome to have such a rectifier circuit and amplifier and management system, while the output of these reported energy harvesters is usually very low.
Furthermore, in the common reports of flexible sensors applied to wearable electronics, it is often necessary to have parts with critical amplification circuitry, which also makes the overall system more complex and inefficient. Secondly, how to integrate multiple sensing modes into one device is another technical difficulty. Most of the above-mentioned multifunctional sensors can realize a combination of two or at most three different sensing modes, while other sensors have relatively large differences.
Disclosure of Invention
The embodiment of the invention provides a multifunctional diode piezoelectric sensor, a preparation method and wearing equipment, wherein the piezoelectric performance is good, the sensitivity is high in a detection mode, and the application detection range is wide; the energy can be collected while detecting, and an external power supply is not needed.
To achieve the above object, in one aspect, an embodiment of the present invention provides a multifunctional diode piezoelectric sensor, including:
the device comprises a flexible substrate, a metal top electrode and a metal oxide conductive bottom electrode, wherein the metal top electrode and the metal oxide conductive bottom electrode are manufactured on the flexible substrate;
the multifunctional diode piezoelectric sensor is provided with a P-N junction diode structure, and the P-N junction diode structure is positioned between a metal top electrode and a metal oxide conductive bottom electrode; the N-type layer of the P-N junction diode structure is arranged below the P-type layer of the P-N junction diode structure;
the N-type layer of the P-N junction diode structure is made of semiconductor piezoelectric materials, and the P-type layer of the P-N junction diode structure is made of organic semiconductors; and a PET passivation layer is packaged on the upper surface of the P-type layer.
In another aspect, an embodiment of the present invention provides a wearable device, where the wearable device includes: basic equipment with dress function and locate the multifunctional diode piezoelectric sensor who has on the basic equipment of dress function, wherein, multifunctional diode piezoelectric sensor includes:
a flexible substrate at the bottom layer for supporting all parts of the entire sensor unit;
a sensor unit over the flexible substrate for detecting one or more of dynamic pressure, static pressure, humidity, and acoustic waves;
the passivation layer is positioned on the sensor unit and packaged on the sensor unit to be used as a contact surface for detecting and sensing; the passivation protection layer adopts a cylindrical texture pattern to improve the sensitivity of the sensor unit;
the sensor unit is of a P-N junction diode structure, an N-type layer of the P-N junction diode structure is made of semiconductor piezoelectric materials, and a P-type layer of the P-N junction diode structure is made of organic semiconductors; the passivation layer is packaged on the upper surface of the P-type layer;
wherein, wearing equipment includes: electronic skin, and clothes.
Furthermore, an embodiment of the present invention provides a method for manufacturing a multifunctional diode piezoelectric sensor, including:
sputtering and depositing a bottom electrode on the top of the flexible substrate;
sputtering a semiconductor piezoelectric material at a radio frequency at room temperature to form an N-type layer of a P-N junction diode structure;
coating a biocompatible organic semiconductor on the N-type layer to form a P-type layer of a P-N junction diode structure;
and dropping metal on the P-type layer by metal evaporation or metal sputtering to serve as a metal top electrode.
The technical scheme has the following beneficial effects: the piezoelectric performance is good, the sensitivity is high in a detection mode, and the detection range is wide; the energy can be collected while detecting, and an external power supply is not needed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a multi-functional diode piezoelectric sensor in accordance with an embodiment of the present invention;
fig. 2 is a flow chart of a method of making a multifunctional diode piezoelectric sensor in accordance with an embodiment of the present invention;
FIG. 3 is an equivalent circuit of FIG. 1;
FIG. 4 is a layout diagram of a design employing the multi-functional diode piezoelectric sensor of FIG. 1 as a human body microelectronics;
FIG. 5 is a schematic diagram showing the current and voltage variations generated by a butterfly landing on top of a multi-function diode piezoelectric sensor;
FIG. 6 is a diagram illustrating the pulse values and the resulting voltage changes of the human body pulse collected by the multifunctional diode piezoelectric sensor according to the embodiment of the present invention;
FIG. 7 is a schematic diagram of the voltage change of humidity collected by the multifunctional diode piezoelectric sensor according to the embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, in connection with an embodiment of the present invention, there is provided a multifunctional diode piezoelectric sensor, including:
the device comprises a flexible substrate, a metal top electrode and a metal oxide conductive bottom electrode, wherein the metal top electrode and the metal oxide conductive bottom electrode are manufactured on the flexible substrate;
the multifunctional diode piezoelectric sensor is provided with a P-N junction diode structure, and the P-N junction diode structure is positioned between a metal top electrode and a metal oxide conductive bottom electrode; the N-type layer of the P-N junction diode structure is arranged below the P-type layer of the P-N junction diode structure;
the N-type layer of the P-N junction diode structure is made of semiconductor piezoelectric materials, and the P-type layer of the P-N junction diode structure is made of organic semiconductors; and a PET passivation layer is packaged on the upper surface of the P-type layer.
Preferably:
the organic semiconductor of the P-type layer includes one of: PEDOT PSS, P3HT, PTAA;
the semiconductor piezoelectric material of the N-type layer is ZnO;
the metal top electrode is made of one of the following materials: gold, platinum, silver, copper;
the material for manufacturing the metal oxide bottom electrode comprises one of the following materials: indium Tin Oxide (ITO) and aluminum-doped zinc oxide (AZO).
Preferably, there is a sensing mode and an energy harvesting mode, wherein:
the sensing mode is realized by the following steps: directly reading the voltage or current of the P-N junction diode structure, and taking the read voltage or current of the P-N junction diode structure as a sensing signal to realize different types of sensing detection; the P-N junction diode structure is used for realizing different types of sensing detection in a sensing mode, wherein the types of the sensing detection comprise: high sensitivity dynamic pressure detection, humidity detection, temperature detection and sound wave detection; the minimum pressure detected in the high-sensitivity dynamic pressure detection or sound wave detection is 0.1N;
acquiring corresponding energy through the energy acquisition mode while detecting in a sensing mode; the energy harvesting mode is realized as follows: the P-N junction diode structure is connected with an energy storage capacitor in parallel, electric charges generated by pressure detection are stored in the energy storage capacitor after being detected by the P-N junction diode structure, and the energy storage capacitor uses the stored electric charges for supplying power to an external circuit.
Preferably, when the semiconductor piezoelectric material of the N-type layer is ZnO, the ZnO is in a dense thin film or one-dimensional nanowire shape, and 002 unit cells of a wurtzite crystal structure possessed by the ZnO are oriented;
when high-sensitivity dynamic pressure detection or acoustic wave detection is carried out, when stress is applied to a PET passivation layer, the stress is polarized in two different directions of ZnO, charges are accumulated on the upper surface and the lower surface of the ZnO, and the ZnO has the optimal piezoelectric response when the 002 unit cells are oriented; and
the ZnO in the shape of a compact film or a one-dimensional nanowire enables the Schottky barrier to increase the energy storage capacitance, and when the ZnO is used for high-sensitivity dynamic pressure detection or sound wave detection, the minimum pressure detected by the P-N junction diode structure is 0.1N.
Preferably, the first and second electrodes are formed of a metal,
during temperature detection, water vapor is absorbed through oxygen vacancies of ZnO, interface charges are generated on an N-type layer and a P-type layer, the interface charges form voltage signals, and humidity sensing is realized by detecting the voltage signals.
In connection with an embodiment of the present invention, there is provided a wearable device including: basic equipment with dress function and locate the multifunctional diode piezoelectric sensor who has on the basic equipment of dress function, wherein, multifunctional diode piezoelectric sensor includes:
a flexible substrate on the bottom layer for supporting all parts of the whole sensor unit;
a sensor unit over the flexible substrate for detecting one or more of dynamic pressure, static pressure, humidity, and acoustic waves;
the passivation layer is positioned on the sensor unit and packaged on the sensor unit to be used as a contact surface for detecting and sensing; the passivation protection layer adopts a cylindrical texture pattern to improve the sensitivity of the sensor unit;
the sensor unit is of a P-N junction diode structure, an N-type layer of the P-N junction diode structure is made of semiconductor piezoelectric materials, and a P-type layer of the P-N junction diode structure is made of organic semiconductors; the passivation layer is packaged on the upper surface of the P-type layer;
wherein, wearing equipment includes: electronic skin, and clothes.
As shown in fig. 2, in combination with the embodiment of the present invention, there is provided a method for manufacturing a multifunctional diode piezoelectric sensor, including:
s101: sputtering and depositing a bottom electrode on the top of the flexible substrate;
s102: sputtering a semiconductor piezoelectric material at a radio frequency at room temperature to form an N-type layer of a P-N junction diode structure;
s103: coating a biocompatible organic semiconductor on the N-type layer to form a P-type layer of a P-N junction diode structure;
s104: and dropping metal on the P-type layer by metal evaporation or metal sputtering to serve as a metal top electrode.
Preferably, the step 101 of sputter depositing the bottom electrode on the top of the flexible substrate specifically includes:
at room temperature, sputtering and depositing Indium Tin Oxide (ITO) on a flexible substrate PET to form a transparent metal oxide conductive bottom electrode, wherein the thickness of the Indium Tin Oxide (ITO) is 100-200 nm;
102, sputtering the semiconductor piezoelectric material at the radio frequency at the room temperature to form an N-type layer of a P-N junction diode structure, specifically including:
performing radio frequency sputtering deposition of a ZnO film on a flexible substrate at room temperature and under the pressure of 1.6Pa and in an argon atmosphere, and performing annealing treatment at 100 ℃ on the sputtered ZnO film to obtain an N-type layer of wurtzite crystal structure ZnO, wherein the thickness of the wurtzite crystal structure ZnO is 0.5-1 mu m; the polycrystal of the wurtzite crystal structure ZnO meets the preset requirement in the 002 unit cell orientation, and the crystal peak intensity in the 002 unit cell orientation meets the preset peak intensity.
Preferably, the coating of the biocompatible organic semiconductor on the N-type layer comprises one of: PEDOT PSS, P3HT, PTAA;
step 103, coating a biocompatible organic semiconductor on the N-type layer to form a P-type layer of a P-N junction diode structure, specifically including:
when the organic semiconductor is PEDOT/PSS, diluting the PEDOT/PSS and deionized water in a ratio of 1:10 to obtain a PEDOT/PSS aqueous solution;
coating a biocompatible PEDOT (Polytetrafluoroethylene) solution on the N-type layer by means of drop coating or screen printing to obtain a P-type layer, wherein the thickness of the P-type layer is thinner than that of the N-type layer; wherein the thickness of the P type layer is 100-180 nm.
Preferably, the step 104 of using metal evaporation or metal sputtering to drop metal on the P-type layer as a metal top electrode specifically includes:
depositing metal with the thickness of 100nm on the P-type layer by utilizing metal evaporation or metal sputtering at room temperature to obtain a metal top electrode; wherein the material of the metal top electrode comprises one of the following materials: gold, platinum, silver, copper;
the preparation method of the multifunctional diode piezoelectric sensor further comprises the following steps:
s105: covering a PET passivation layer with the thickness of 50 mu m on the upper surface of the P-type layer except the metal top electrode to package the P-type layer; the PET passivation layer is provided with cylindrical voids to enable humidity sensing.
The above technical solutions of the embodiments of the present invention are described in detail below with reference to specific application examples, and reference may be made to the foregoing related descriptions for technical details that are not described in the implementation process.
The invention relates to a multifunctional diode piezoelectric sensor and a preparation process thereof, aiming at solving the technical problems that:
1. multi-sensing mode of high sensitivity. The piezoelectric performance is good, and a plurality of important sensing modes are integrated into a unique device, so that the pressure (0.1-10 Newton value) of landing and taking off of mosquitoes or butterflies on the device can be detected.
2. No complex rectifier circuit design is required. From the power supply, most common and widely used sensors and energy harvesters are affected by the circuit design because their output voltage or current will not meet the requirements of the appropriate power management circuitry or readout circuitry for harvesting. The P-N structure (P-N junction diode structure) presented in this patent overcomes such problems in the previous modes, since it does not require any signal rectification, which makes the system simple and practical.
3. Easy to make and use. Compared with the prior art, the P-N structure has lower realization cost. The core of the P-N junction structure is a piezoelectric material, such as ZnO as an N-type material; and common P-type materials such as: PEDOT PSS, PTAA and nickel oxide are widely used because of their relatively low price. Zn is one of the essential trace elements for human body, and PEDOT PSS also has good biocompatibility. Therefore, the device is not only very humanized and has no side effect on human body (such as when used for electronic skin), but also can protect human body. This type of P-N structure is also relatively simple to manufacture, which is another advantage that helps to reduce manufacturing time and cost.
4. High stability and high reliability. Since the ZnO ferroelectric oriented in the 002 direction has a reliable and stable behavior under strain or stress, the device can withstand almost more than 20000 high-strength duty cycles without degradation of performance.
5. Is friendly to users and environment. As described above, in order to form a P-N structure, an N-type material of ZnO and a P-type material of PEDOT: PSS are used.
The multifunctional device based on the P-N junction (P-N junction diode structure) provided by the invention has four sensing modes: high sensitivity pressure sensing, humidity sensing, temperature sensing, acoustic wave sensing, and in addition, very excellent performance in terms of piezoelectric sensitivity. Therefore, this concept has a wide potential for applications, such as electronic skin, which enables force, temperature, humidity, sonic and body pulse detection. The sensing function and the energy collecting function can be combined, namely, the generated voltage signal is large enough to be well detected and stored, the collected energy is stored in a matched super capacitor, and finally the collected energy can be used for supplying power to some low-power electronic devices, such as Radio Frequency Identification (RFID) and the like. In one aspect, in human health monitoring applications, some mechanical motion of a human (e.g., joint bending) may be utilized to harvest energy and wake up the RFID tag. On the other hand, the sensing mode of the structure can detect heartbeat pulses and the like, and the sensing and energy collecting functions of a single device are realized at the same time.
The device with the P-N junction structure is prepared by combining the N-type semiconductor piezoelectric material layer and the P-type semiconductor organic polymer material layer, and has two working modes: a sensing mode and an energy harvesting mode. The device can realize energy collection and sensing at the same time, can realize self power supply during working, does not need an external power supply, and can monitor pressure, humidity and temperature. The PEDOT, PSS and ZnO are both biocompatible materials, so that the prepared P-N junction device is also an environment-friendly and user-friendly sensor/collector. The self-powered sensing device has wide requirements in the aspects of human health monitoring, infrastructure monitoring and the like.
The device (i.e. the multifunctional diode piezoelectric sensor) has a P-N junction diode structure, wherein the structure of the P-N junction keeps the N type as ZnO, and the P type layer is realized by a semiconductor conducting polymer, is provided with a metal top electrode and a metal oxide conducting bottom electrode, and is manufactured on a flexible substrate. The multifunctional diode piezoelectric sensor is provided with a P-N junction diode structure, and the P-N junction diode structure is positioned between a metal top electrode and a metal oxide conductive bottom electrode; the N-type layer of the P-N junction diode structure is arranged below the P-type layer of the P-N junction diode structure; the N-type layer of the P-N junction diode structure is made of semiconductor piezoelectric materials, and the P-type layer of the P-N junction diode structure is made of organic semiconductors; and a PET passivation layer is packaged on the upper surface of the P-type layer.
The P-type layer can be one of organic semiconductors such as PEDOT, PSS, P3HT, PTAA and the like, the metal oxide conductive bottom electrode can be composed of Indium Tin Oxide (ITO) or aluminum-doped zinc oxide (AZO), and the metal top electrode is composed of one of gold, platinum, silver and copper.
The manufacturing process of the multifunctional diode piezoelectric sensor can be realized by the following simple standard steps: sputtering and depositing a bottom electrode on the top of the flexible substrate, performing radio frequency sputtering on a piezoelectric material ZnO at room temperature, spin-coating PEDOT (PSS), and finally evaporating gold to be used as a top electrode.
The P-N junction device (P-N junction diode structure) can realize a variety of different types of sensing under the sensing mode: dynamic pressure detection, humidity detection and sound wave detection. The sensing mode is realized by the following steps: and directly reading the voltage or the current of the P-N junction as a sensing signal. In the energy collection mode of the proposed P-N junction device, any applied pressure and energy generated by vibration can be collected. The combination of sensing and energy harvesting is truly achieved, thereby realizing the concept of a self-driven, battery-less sensor. The energy harvesting mode is implemented as follows: the PN junction is connected with an energy storage capacitor in parallel, electric charges generated by piezoelectricity are stored in the capacitor firstly, then the capacitor supplies power to an external circuit and serves as a power supply of the multifunctional diode piezoelectric sensor, and the self-driven sensor without a battery is achieved.
The technical scheme of the invention is described in detail as follows:
1. FIG. 1 is a schematic cross-sectional view of a P-N structure formed by ZnO and PEEDOT PSS. The P-N junction structure is formed by sandwiching (optimizable) a 1 μm layer of ZnO of an N-type piezoelectric material and a 200nm layer of a P-type polymer (e.g., PEDOT: PSS) between bottom and top electrodes, which are 150nm thick indium tin oxide ITO and 50-150nm thick metal layers, respectively, which can be gold, silver, platinum, copper, etc. Numbers (0) to (5) in fig. 1 are respectively represented as: 0: a PET substrate; 1: an ITO layer; 2: an N-type layer (ZnO layer); 3: a P-type layer (P3HT layer, 120-; 4: a metal top electrode layer; 5: a PET encapsulation layer (PET is polyethylene terephthalate).
2. When any mechanical stress is applied to the device (lightly touched on top of the structure as shown in fig. 1), when the N-type layer semiconductor is presentWhen the piezoelectric material is ZnO, the stress will polarize in two different directions, where charge will build up on the upper and lower surface areas of the ZnO. Furthermore, ZnO as a piezoelectric material of a semiconductor can be made into a dense thin film or a one-dimensional nanowire (1D for short)Shape of) Because ZnO has a wurtzite crystal structure, ZnO crystals can obtain the best piezoelectric response when oriented in the 002 direction (the 002 direction is an industry term) of the unit cell compared to other semiconductor piezoelectric materials. However, in the case of a piezoelectric material, when ZnO is subjected to a voltage and is not subjected to a voltage according to its electrical behavior, the capacitance of the material with a thickness of 500nm is not changed (the capacitance is not changed because the deformation is negligible with respect to the thickness). The P-N junction or schottky barrier made with ZnO of the foregoing characteristics increases the capacitance of the overall device, wherein any change caused by pressure on the Schottky Barrier Height (SBH) results in an increase in capacitance. The static sensitivity of the P-N junction diode structure is very high and even a weight of about 1g can be detected well. On the other hand, the dynamic pressure response on the P-N junction diode structure can be characterized according to the piezoelectric effect of the piezoelectric N-type material. Using PEDOT: PSS as a P-type barrier allows the fabrication of a diode because of its high work function. Therefore, not only the charge will be polarized in the N-type ZnO but also the height of the schottky barrier will change due to any applied stress or strain, thereby realizing a very high sensitivity dynamic pressure sensor capable of detecting a force of 0.1N. A typical butterfly landing and takeoff is therefore detected weighing approximately 0.5-1g, and fig. 5 illustrates the extraction of a dc voltage when the butterfly lands on top of the sensor and takes off after a period of time.
In summary, ZnO is an oxide, so it inevitably has oxygen vacancies during its growth, which is the oxide material, but most of the oxides are insulators, and ZnO is an N-type semiconductor, so it can be used as a PN junction. Finally, ZnO growing in the 002 direction has good piezoelectric property, so that the ZnO can be manufactured into a PN junction diode for measuring pressure and sound pressure. Meanwhile, the oxygen vacancy has water absorption capacity, and the conductivity of the zinc oxide is changed, so that the humidity can be measured. And is thus multifunctional.
The introduction of the P-N structure brings an intrinsic built-in capacitance to the system. In this case we have two types of capacitors in series, corresponding to the dielectric ZnO layer and the P-N junction schottky barrier, respectively. The increase in the overall capacitance of such capacitance-based pressure sensors results in reduced sensitivity, while it also improves the linear behavior of the capacitance, particularly in static pressure sensing. Therefore, a trade-off is made between these two effects depending on the field of practical application. Increasing the thickness of the P-type material (PEDOT: PSS) increases the capacitance, while the sensitivity of the device at low static voltages decreases. The thickness of the P-type layer needs to be optimized and balanced by suitable manufacturing techniques.
3. Fig. 3(a) first depicts the equivalent circuit, and fig. 3(b) also depicts the operation of the device in the energy harvesting mode. Wherein the P-N junction structure can be modeled as two junction capacitances (C)JAnd diffusion capacitance (C)d) And a shunt resistor (R) as a junctionJ) Are connected in parallel. RSIs the resistance associated with all ohmic contacts, wires, etc. ZnO itself as a dielectric layer can also be equivalent to a simple model in which a bulk material (C) is introducedZ) Related capacitance and resistance (R)Z)。
4. Inspired by human skin tissue structure, wearable devices (such as electronic skins) are one of the applications of such multifunctional devices. Fig. 4(a) and (b) illustrate an analogy of human skin to a proposed design layout. The electronic skin is similar to human skin tissues and mainly comprises three layers. The bottom layer is a flexible substrate that supports all parts of the entire sensor. The second layer at the bottom is a sensor unit, above the flexible substrate, capable of detecting one or more of dynamic/static pressure, humidity and sound waves. The top is a passivation protective layer, which is arranged on the sensor unit and is packaged on the sensor unit to be used as a contact surface for detecting and sensing; it is patterned into a cylindrical texture to improve the sensitivity of the device while serving as an encapsulation layer. A schematic of this structure can be seen in fig. 1, with a light touch pressure applied to the top of the structure. The sensor unit is of a P-N junction diode structure, an N-type layer of the P-N junction diode structure is made of semiconductor piezoelectric materials, and a P-type layer of the N-junction diode structure is made of organic semiconductors; the passivation layer is packaged on the upper surface of the P-type layer.
5. The ability of such a device to detect a human pulse in a sensing mode is best illustrated in fig. 6. The P1, P2 peaks (peak pressure in systolic and diastolic phases, respectively) corresponding to cardiac function are seen in the detected complete signal, from which further analysis and diagnosis can be made. A number of different locations may be selected to obtain the pulse signals, such as: wrist, neck, ankle and elbow.
6. Fig. 7 shows the signal obtained by humidity. It describes how the P-N junction diode structure responds to humidity and the peak voltage drops during the sensing recovery time, and the detection signal is obtained without an external power supply.
The manufacturing process of the device of the invention is as follows:
a) an ITO transparent electrode was deposited on a flexible substrate PET (0). This step can be achieved by sputtering techniques. The ITO bottom electrode has a thickness of typically 100 to 200nm, and the transparent electrode sputtered at room temperature has very excellent conductivity. Since the PET substrate can only withstand temperatures of about 150 degrees celsius, all preparation steps must be accomplished by a low temperature process, e.g., room temperature.
b) Under the pressure of 1.6Pa and the argon atmosphere, ZnO with the thickness of about 1 μm is deposited by RF sputtering under the condition of room temperature. After deposition, XRD analysis is carried out to check whether ZnO crystals are well oriented in the 002 direction; since ZnO belongs to the hexagonal system, whether the crystal orientation thereof is in the 002 direction plays an important role in obtaining the optimum piezoelectric response. The strength of the piezoelectric response is affected by the piezoelectric coefficients of d33 and d31 in the 33 and 31 directions. The crystal orientation 002 direction of the wurtzite crystal structure obtained by optimizing sputtering can improve the piezoelectric coefficient and obtain better response when stress is applied.
c) The ZnO sputtered on the flexible substrate is subjected to annealing treatment at 100 ℃, so that the obtained wurtzite ZnO (wurtzite crystal structure ZnO) polycrystal has better 002 crystal orientation and peak crystal strength in the direction. Thereby further enhancing the piezoelectric performance of the device as it corresponds to that of a ZnO film. The preparation of the ZnO hexagonal polycrystal with good 002 crystal orientation is challenging, and the sputtering condition is well controlled.
d) A biocompatible P-type layer, such as PEDOT: PSS, is applied by drop coating or screen printing. Some preparation of PEDOT: PSS is usually required because its acidity etches other materials (metals, oxides), especially PSS components. Some preparations were made for PEDOT: PSS as follows: since PEDOT: PSS is water soluble, it was diluted with deionized water at a ratio of 1:10 in deionized water. PSS is sufficient to drop or screen print on ZnO. The thickness of the P-type layer is thinner than that of the piezoelectric layer, and is about 100-180 nm. The PET/ITO surface is relatively hydrophobic, PEDOT: PSS is difficult to coat on, while thick layers of ZnO on ITO have better surface hydrophilicity and form a proper connection between N-type and P-type materials.
e) Copper was deposited as a top electrode at a thickness of 100 nm. The top electrode can be made of gold or copper and silver, and copper with good binding energy and practicability is generally selected as the top electrode. The deposition of the above copper electrodes must be carried out at low temperature (less than 150 degrees celsius) to prevent mechanical deformation or damage of the PET substrate. This process can be accomplished by evaporation or sputter deposition of the metal at room temperature.
f) Finally, a 50 μm thick passivation layer of PET was used on top of the device to encapsulate the PEDOT: PSS layer. PSS is water soluble, and this passivation helps reduce static charge and protect the P-type layer. In addition, since the mechanism of humidity sensing relies on filling oxygen vacancies in the ZnO layer, a cylindrical texture pattern is applied on the passivation layer to achieve humidity sensing. This helps the device to correctly detect the oxygen transmitted to the device through the cylindrical hole while filtering out water to protect the P-type layer. The PEDOT and PSS as P-type materials can influence the humidity sensing mechanism, meanwhile, the absorption of oxygen is enhanced, and voltage signals with larger amplitude and higher response compared with pure ZnO humidity sensors can be obtained.
The reasonable structural design of the device enables a simple and rapid preparation flow to be one of the advantages of the invention, the preparation can be completed quickly in less than one day, and the manufacturer can better and more easily understand the preparation process so as to improve the product in the future.
The technical scheme of the invention comprises the following alternative modes of parts or steps:
the proposed concept of forming P-N structures by using piezoelectric material semiconductors as sensing and collecting means may involve some modifications and substitutions in the design layout of the device structure, particularly in some manufacturing steps. The N-type material in the device is ZnO ferroelectric piezoelectric material, but it can be replaced by various other N-type materials in semiconductors, such as PZT piezoelectric ceramic materials. But PZT is rigid and bulky, and such devices can present certain problems in flexibility. In this sense, ZnO shows better flexibility compared to PZT. The higher piezoelectric coefficients d33 and d31 of PZT theoretically given, compared to ZnO, improve the response and output signal of the device, but their lack of flexibility can be troublesome for wearable applications.
In addition, PSS, a biocompatible material, is given as the P-type material in the P-N structure. Regardless of user-friendliness and biocompatibility, it can be replaced with various P-type materials to form PN junctions, such as: and (3) nickel oxide. In this case, the efficiency and output of the device in the energy harvesting mode play a crucial role. The current may be low and the response signal output may be imperfect, both of which directly affect the output power and thus efficiency, subject to the conductivity of certain given materials. Therefore, it is necessary to optimize the material selection according to the application in a specific situation, and different N-type or P-type materials may be used in different applications.
With respect to the device fabrication steps mentioned in the previous section, several alternatives are possible due to the various well-established fabrication process techniques. Layer 2 in the device fabrication of fig. 1 is the deposition of a ZnO thick film, which can be done simply by rf sputtering. Whereas ZnO spin coating and subsequent annealing based on a solution method may be considered as an alternative to the sputtering process. Likewise, ZnO spin coating based on a solution method requires optimization of the crystal orientation of ZnO polycrystals during annealing. Another method of ZnO deposition is to first sputter a very thin seed layer, e.g. 5nm, and then deposit ZnO on top of the seed layer by solution spin coating, which helps the crystallization of the ferroelectric.
PSS, coating, which is the case in figure 1, can be accomplished by several alternative techniques, such as: spin coating, screen printing, drop coating, and doctor blading.
The 4 th layer in fig. 1 is a metal evaporated as top contact, but could simply be replaced by some other metal film tape. Although this type of tape does not perform well in terms of atomic bonding and reaction, the efficiency of the device may be low. Another potentially more practical approach compared to the technique of metal evaporation is to sputter deposit the top electrode.
The invention belongs to the technical field of: flexible electronics, nanotechnology, microelectronics, sensors; the method can be specifically used for: tactile sensors, wearable energy harvesters, electronic skins, vibration generators, electronic skins, wearable electronics, and the like. The method comprises the following specific steps:
the use of wearable devices and electronic skin sensing modalities helps to simulate almost all of the necessary functions of human skin. Meanwhile, the sensing mode can also be used for monitoring some vital signs, such as pulse signals, and the energy collection mode of the equipment collects energy from human body movement to wake up some low-power-consumption RFID reading circuits, so that detected signals are wirelessly transmitted. Meanwhile, the two modes can work and operate simultaneously, and can be introduced into a plurality of fields as battery-free equipment. For example, an elbow patch for measuring blood pressure can be attached to the elbow to collect mechanical energy of arm bending and simultaneously realize pulse monitoring.
Wearable device aspects, such as apparel. Wherein, the shoes can carry out specific measurement to everyone's foot pressure, the area of the biggest applied pressure, humidity etc to some professional intelligent shoes can be customized to produce according to this, be used for some sportsmen of any event. It may also be considered a custom made foot cover to improve comfort and achieve foot care. The foot is also considered to be the second heart of the human body, and the health of the human body is usually affected by whether the foot is healthy or not.
In some remote areas, vibration-based infrastructure (e.g. bridges) require some sort of fault checking, in which case sensors may be used, but the cost of requiring periodic battery replacement and maintenance in such systems can be somewhat burdensome. The concept of the device proposed above, which can simultaneously perform sensing and energy harvesting, is well suited for these infrastructures for fault monitoring.
It should be understood that the specific order or hierarchy of steps in the processes disclosed is an example of exemplary approaches. Based upon design preferences, it is understood that the specific order or hierarchy of steps in the processes may be rearranged without departing from the scope of the present disclosure. The accompanying method claims present elements of the various steps in a sample order, and are not intended to be limited to the specific order or hierarchy presented.
In the foregoing detailed description, various features are grouped together in a single embodiment for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments of the subject matter require more features than are expressly recited in each claim. Rather, as the following claims reflect, invention lies in less than all features of a single disclosed embodiment. Thus, the following claims are hereby expressly incorporated into the detailed description, with each claim standing on its own as a separate preferred embodiment of the invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. To those skilled in the art; various modifications to these embodiments will be readily apparent, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
What has been described above includes examples of one or more embodiments. It is, of course, not possible to describe every conceivable combination of components or methodologies for purposes of describing the aforementioned embodiments, but one of ordinary skill in the art may recognize that many further combinations and permutations of various embodiments are possible. Accordingly, the embodiments described herein are intended to embrace all such alterations, modifications and variations that fall within the scope of the appended claims. Furthermore, to the extent that the term "includes" is used in either the detailed description or the claims, such term is intended to be inclusive in a manner similar to the term "comprising" as "comprising" is interpreted when employed as a transitional word in a claim. Furthermore, any use of the term "or" in the specification of the claims is intended to mean a "non-exclusive or".
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A multi-function diode piezoelectric sensor, comprising: the device comprises a flexible substrate, a metal top electrode and a metal oxide conductive bottom electrode, wherein the metal top electrode and the metal oxide conductive bottom electrode are manufactured on the flexible substrate;
the multifunctional diode piezoelectric sensor is provided with a P-N junction diode structure, and the P-N junction diode structure is positioned between a metal top electrode and a metal oxide conductive bottom electrode; the N-type layer of the P-N junction diode structure is arranged below the P-type layer of the P-N junction diode structure;
the N-type layer of the P-N junction diode structure is made of semiconductor piezoelectric materials, and the P-type layer of the P-N junction diode structure is made of organic semiconductors; and a PET passivation layer is packaged on the upper surface of the P-type layer.
2. The multi-function diode piezoelectric sensor of claim 1, wherein:
the organic semiconductor of the P-type layer comprises one of: PEDOT PSS, P3HT, PTAA;
the semiconductor piezoelectric material of the N-type layer is ZnO;
the metal top electrode is made of one of the following materials: gold, platinum, silver, copper;
the material for manufacturing the metal oxide bottom electrode comprises one of the following materials: indium Tin Oxide (ITO) and aluminum-doped zinc oxide (AZO).
3. The multi-function diode piezoelectric sensor of claim 1, having a sensing mode and an energy harvesting mode, wherein:
the sensing mode is realized by the following steps: directly reading the voltage or the current of the P-N junction diode structure, and taking the read voltage or the read current of the P-N junction diode structure as a sensing signal to realize different types of sensing detection; the P-N junction diode structure is used for realizing different types of sensing detection in a sensing mode, wherein the types of the sensing detection comprise: high sensitivity dynamic pressure detection, humidity detection, temperature detection and sound wave detection; the minimum pressure detected in the high-sensitivity dynamic pressure detection or sound wave detection is 0.1N;
acquiring corresponding energy through the energy acquisition mode while detecting in a sensing mode; the energy collection mode is realized as follows: the P-N junction diode structure is connected with an energy storage capacitor in parallel, charges generated by pressure detection are stored in the energy storage capacitor after being detected by the P-N junction diode structure, and the stored charges are used for supplying power to an external circuit by the energy storage capacitor.
4. The multi-functional diode piezoelectric sensor according to claim 3, wherein when the semiconductor piezoelectric material of the N-type layer is ZnO, the ZnO is in a dense thin film or one-dimensional nanowire shape, and is in 002 unit cell orientation of wurtzite crystal structure possessed by the ZnO;
when high-sensitivity dynamic pressure detection or acoustic wave detection is carried out, when stress is applied to a PET passivation layer, the stress is polarized in two different directions of ZnO, charges are accumulated on the upper surface and the lower surface of the ZnO, and the ZnO has the optimal piezoelectric response when the 002 unit cells are oriented; and
the ZnO in the shape of a compact film or a one-dimensional nanowire enables the Schottky barrier to increase the energy storage capacitance, and when the ZnO is used for high-sensitivity dynamic pressure detection or sound wave detection, the minimum pressure detected by the P-N junction diode structure is 0.1N.
5. The multi-functional diode piezoelectric sensor of claim 4,
during temperature detection, water vapor is absorbed through oxygen vacancies of ZnO, interface charges are generated on an N-type layer and a P-type layer, the interface charges form voltage signals, and humidity sensing is realized by detecting the voltage signals.
6. A wearable device, characterized in that the wearable device comprises: basic equipment with dress function and locate the multifunctional diode piezoelectric sensor who has on the basic equipment of dress function, wherein, multifunctional diode piezoelectric sensor includes:
a flexible substrate at the bottom layer for supporting all parts of the entire sensor unit;
a sensor unit over the flexible substrate for detecting one or more of dynamic pressure, static pressure, humidity, and acoustic waves;
the passivation layer is positioned on the sensor unit and packaged on the sensor unit to be used as a contact surface for detecting and sensing; the passivation protection layer adopts a cylindrical texture pattern to improve the sensitivity of the sensor unit;
the sensor unit is of a P-N junction diode structure, an N-type layer of the P-N junction diode structure is made of semiconductor piezoelectric materials, and a P-type layer of the P-N junction diode structure is made of organic semiconductors; the passivation layer is packaged on the upper surface of the P-type layer;
wherein, wearing equipment includes: electronic skin, and clothes.
7. A preparation method of a multifunctional diode piezoelectric sensor is characterized by comprising the following steps:
sputtering and depositing a bottom electrode on the top of the flexible substrate;
sputtering a semiconductor piezoelectric material at a radio frequency at room temperature to form an N-type layer of a P-N junction diode structure;
coating a biocompatible organic semiconductor on the N-type layer to form a P-type layer of a P-N junction diode structure;
and using metal evaporation or metal sputtering to drop metal on the P type layer to be used as a metal top electrode.
8. The method for preparing a multifunctional diode piezoelectric sensor according to claim 7, wherein the step of sputter depositing a bottom electrode on top of a flexible substrate comprises:
at room temperature, sputtering and depositing Indium Tin Oxide (ITO) on a flexible substrate PET to form a transparent metal oxide conductive bottom electrode, wherein the thickness of the Indium Tin Oxide (ITO) is 100-200 nm;
the method for forming the N-type layer of the P-N junction diode structure by radio-frequency sputtering of the semiconductor piezoelectric material at room temperature specifically comprises the following steps:
performing radio frequency sputtering deposition on a ZnO film on a flexible substrate at room temperature and under the pressure of 1.6Pa and in an argon atmosphere, and performing annealing treatment at 100 ℃ on the sputtered ZnO film to obtain an N-type layer of wurtzite crystal structure ZnO, wherein the thickness of the wurtzite crystal structure ZnO is 0.5-1 mu m; the polycrystal of the wurtzite crystal structure ZnO meets the preset requirement in the 002 unit cell orientation, and the crystal peak intensity in the 002 unit cell orientation meets the preset peak intensity.
9. The method of claim 7, wherein coating the biocompatible organic semiconductor on the N-type layer comprises one of: PEDOT PSS, P3HT, PTAA;
the method for forming the P-type layer of the P-N junction diode structure by coating the biocompatible organic semiconductor on the N-type layer specifically comprises the following steps:
when the organic semiconductor is PEDOT/PSS, diluting the PEDOT/PSS and deionized water in a ratio of 1:10 to obtain a PEDOT/PSS aqueous solution;
PSS aqueous solution is coated on the N-type layer by drop coating or screen printing to obtain a P-type layer, wherein the thickness of the P-type layer is thinner than that of the N-type layer; wherein the thickness of the P type layer is 100-180 nm.
10. The method for preparing a multifunctional diode piezoelectric sensor according to claim 7, wherein the step of depositing metal on the P-type layer by metal evaporation or metal sputtering as a metal top electrode comprises:
depositing metal with the thickness of 100nm on the P-type layer by utilizing metal evaporation or metal sputtering at room temperature to obtain a metal top electrode; wherein the material of the metal top electrode comprises one of the following materials: gold, platinum, silver, copper;
the preparation method of the multifunctional diode piezoelectric sensor further comprises the following steps:
covering a PET passivation layer with the thickness of 50 mu m on the upper surface of the P-type layer except the metal top electrode to package the P-type layer; the PET passivation layer is provided with cylindrical voids to enable humidity sensing.
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