CN113013334A - Photoelectric conversion device and preparation method, device and system thereof - Google Patents
Photoelectric conversion device and preparation method, device and system thereof Download PDFInfo
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- CN113013334A CN113013334A CN202110161160.4A CN202110161160A CN113013334A CN 113013334 A CN113013334 A CN 113013334A CN 202110161160 A CN202110161160 A CN 202110161160A CN 113013334 A CN113013334 A CN 113013334A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/18—Applying electric currents by contact electrodes
- A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
- A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
- A61N1/372—Arrangements in connection with the implantation of stimulators
- A61N1/378—Electrical supply
- A61N1/3787—Electrical supply from an external energy source
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a photoelectric conversion device and a preparation method, a device and a system thereof. The flexible substrate and the flexible packaging layer are made of materials which are good in flexibility and small in size, and do not cause inflammatory reaction and influence the performance of an electrical stimulation system; on the basis of the photovoltaic effect principle, the perovskite flexible photoelectric conversion device with high response characteristic under weak light is used for wirelessly supplying power to electronic devices such as flexible stimulation electrodes, the problem of battery capacity is solved, and the batteries do not need to be replaced through an operation; the wireless power supply technology utilizing the photovoltaic effect principle has no electromagnetic compatibility problem on electronic devices in or around the body, and can be widely applied to the field of medical electrical stimulation equipment.
Description
Technical Field
The invention relates to the field of medical electrical stimulation equipment, in particular to a photoelectric conversion device and a preparation method, a device and a system thereof.
Background
The electrical stimulation therapy is widely used for deep brain electrical stimulation, cortical stimulation, spinal cord electrical stimulation, peripheral nerve stimulation, vagus nerve stimulation, percutaneous muscle stimulation and the like, and clinically recovers body functions of patients and effectively improves life quality.
The existing electrical stimulation devices have the following problems: firstly, the materials used by the existing electrostimulation device have high rigidity and large volume, and can generate bulges at the implanted part to cause inflammatory reaction, and sheath tissues are generated around the implant to influence the performance of the electrostimulation system; secondly, the battery capacity carried by the existing electrical stimulation devices and systems is limited; after the battery is exhausted, the battery needs to be replaced through operation; wireless charging technology, which relies on the principle of electromagnetic induction, has electromagnetic compatibility issues for electronic devices in or around the body.
Disclosure of Invention
To solve the above technical problem, an embodiment of the present invention aims to: provided are a photoelectric conversion device, and a method, an apparatus, and a system for manufacturing the same.
The technical scheme adopted by the embodiment of the invention on the one hand is as follows:
a photoelectric conversion device, comprising:
a transparent conductive electrode layer;
a flexible substrate disposed on one side of the transparent conductive electrode layer;
a first charge transport layer disposed on a side of the transparent conductive electrode layer away from the flexible substrate;
the perovskite light absorption layer is arranged on one side, far away from the transparent conductive electrode layer, of the first charge transmission layer;
a second charge transport layer disposed on a side of the perovskite light absorbing layer distal from the first charge transport layer;
a first electrode disposed on a side of the second charge transport layer distal from the perovskite light absorbing layer;
the flexible packaging layer is made of a biocompatible material with high transmittance on target light;
the flexible encapsulation layer encapsulates the first electrode, the second charge transport layer, the perovskite light absorption layer, the first charge transport layer, the transparent conductive electrode layer, and the flexible substrate; or the flexible packaging layer and the flexible substrate form a protective layer, and the first electrode, the second charge transmission layer, the perovskite light absorption layer, the first charge transmission layer and the transparent conductive electrode layer are wrapped by the protective layer.
Optionally, the first charge transport layer is prepared from at least one of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly [ bis (4-phenyl) (4-butylphenyl) amine ], 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline, or nickel oxide;
the second charge transport layer is prepared from a first material and a second material, the first material comprises fullerene, [6, 6] -phenyl-C61-isopropyl butyrate or any one of 56,60:2,3] [5,6] fullerene-C60-IH, and the second material comprises any one of 2, 9-dimethyl-4, 7 diphenyl-1, 10-phenanthroline or tin dioxide; or the second charge transport layer is prepared by adopting at least one material of poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] or 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene.
Optionally, the perovskite light absorption layer is a perovskite light absorption layer, the thickness of the perovskite light absorption layer is 250-2000 nm, the optical forbidden bandwidth of the perovskite light absorption layer is 0.1-5.0 ev, and the spectral response range of the perovskite light absorption layer is 248-12400 nm.
The technical scheme adopted by the embodiment of the invention on the other hand is as follows:
a production method of a photoelectric conversion device, the production method comprising:
preparing a transparent conductive electrode on a flexible substrate;
preparing a first charge transport layer on the transparent conductive electrode;
preparing a perovskite light absorption layer on the first charge transport layer;
preparing a second charge transport layer on the perovskite light absorption layer;
preparing a first electrode on the second charge transport layer;
preparing a flexible packaging layer, wherein the flexible packaging layer is made of a biocompatible material with high transmittance on target light;
the flexible encapsulation layer encapsulates the first electrode, the second charge transport layer, the perovskite light absorption layer, the first charge transport layer, the transparent conductive electrode layer, and the flexible substrate; or the flexible packaging layer and the flexible substrate form a protective layer, and the first electrode, the second charge transmission layer, the perovskite light absorption layer, the first charge transmission layer and the transparent conductive electrode layer are wrapped by the protective layer.
Further, the preparing a first charge transport layer on the transparent conductive electrode includes:
depositing at least one material selected from (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly [ bis (4-phenyl) (4-butylphenyl) amine ], 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline, nickel oxide and tin dioxide on the transparent conductive electrode by using a spin coating method or a vacuum evaporation method to obtain a hole transport layer as a first charge transport layer, wherein the thickness of the hole transport layer is 2-100 nm;
or depositing a tin dioxide layer on the transparent conductive electrode by adopting a spin coating method or an atomic layer deposition method, and annealing the tin dioxide layer at 30-100 ℃ to obtain the annealed tin dioxide layer serving as a first charge transport layer, wherein the thickness of the tin dioxide layer is 2-100 nanometers.
Further, the preparing the perovskite light absorption layer on the first charge transport layer comprises:
preparing a perovskite light absorption layer on the first charge transport layer by a spin coating method, and carrying out laser treatment on the perovskite at a temperature of between 30 and 100 DEG C
Annealing the light absorption layer;
or preparing a perovskite light absorption layer on the first charge transmission layer by adopting a vacuum deposition method;
wherein the optical forbidden band width of the perovskite light absorption layer is 0.1-5.0 electron volt, and the spectral response range of the perovskite light absorption layer is 248-12400 nanometers.
Further, the preparing a second charge transport layer on the perovskite light absorption layer comprises:
depositing a first material and a second material on the surface of the perovskite light absorption layer to obtain a second charge transport layer, wherein the first material comprises any one of fullerene, [6, 6] -phenyl-C61-butyric acid isopropyl ester or 56,60:2,3] [5,6] fullerene-C60-IH, and the second material comprises any one of 2, 9-dimethyl-4, 7 diphenyl-1, 10-phenanthroline or tin dioxide;
or, depositing at least one material of poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] or 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene on the surface of the perovskite light absorption layer by adopting a solution method or a vacuum thermal evaporation method to obtain the second charge transport layer.
The technical scheme adopted by the embodiment of the invention on the other hand is as follows: an apparatus, the apparatus comprising:
the photoelectric conversion device is used for supplying power to the flexible stimulation electrode.
The technical scheme adopted by the embodiment of the invention on the other hand is as follows:
a system, the system comprising:
the photoelectric conversion device is used for receiving and converting the target light into electric energy;
and the flexible stimulation electrode is connected with the photoelectric conversion device and used for generating an electrical stimulation signal under the action of the electric energy.
Optionally, the system further comprises at least one of:
the electric stimulator is used for controlling the light source to generate the target light transmitted to the photoelectric conversion device or generating the electric stimulation signal transmitted to the flexible stimulation electrode;
the flexible energy storage device is used for storing the electric energy generated by the photoelectric conversion device and supplying power to the flexible stimulation electrode;
and the flexible extension lead is used for connecting the photoelectric conversion device and the flexible stimulation electrode or connecting the electric stimulator and the flexible stimulation electrode.
Optionally, the system is any one of an entirely implantable flexible radio stimulation system or a flexible radio stimulation system with a non-implantable electrical stimulator or a flexible radio stimulation system with a non-implantable flexible stimulation electrode.
Optionally, when the system is an integrally implanted flexible wireless electrical stimulation system, the photoelectric conversion device is an implanted photoelectric conversion device, the flexible stimulation electrode is an implanted flexible stimulation electrode, and the electrical stimulator is an implanted electrical stimulator, and the implanted electrical stimulator is configured to generate the electrical stimulation signal sent to the flexible stimulation electrode under the action of the electrical energy.
Optionally, when the system is a flexible wireless electrical stimulation system with a non-implanted electrical stimulator, the photoelectric conversion device is an implanted photoelectric conversion device, the flexible stimulation electrode is an implanted flexible stimulation electrode, and the electrical stimulator is a non-implanted electrical stimulator, and the non-implanted electrical stimulator is configured to control a light source to generate the target light sent to the photoelectric conversion device.
Optionally, when the system is a flexible wireless electrical stimulation system with a non-implanted flexible stimulation electrode, the photoelectric conversion device is a non-implanted photoelectric conversion device, the flexible stimulation electrode is a non-implanted flexible stimulation electrode, and the electrical stimulator is a non-implanted electrical stimulator, and the non-implanted electrical stimulator is configured to control a light source to generate the target light sent to the photoelectric conversion device.
Optionally, the base material in the implantable flexible stimulation electrode and/or the flexible extension lead is a wet tissue adhesive gel; alternatively, the implantable flexible stimulation electrode and the flexible extension lead are made of biocompatible and biodegradable materials.
The flexible perovskite photoelectric conversion device is composed of the flexible substrate, the transparent conductive electrode layer, the first charge transmission layer, the perovskite light absorption layer, the second charge transmission layer, the first electrode and the flexible packaging layer, the flexible substrate and the flexible packaging layer are made of good materials, the size is small, and inflammation reaction cannot be caused and the performance of an electric stimulation system cannot be influenced; on the basis of the photovoltaic effect principle, the perovskite flexible photoelectric conversion device with high response characteristic under weak light is used for wirelessly supplying power to electronic devices such as flexible stimulation electrodes, the problem of battery capacity is solved, and the batteries do not need to be replaced through an operation; the wireless power supply technology utilizing the photovoltaic effect principle has no electromagnetic compatibility problem on electronic devices in or around the body.
According to the preparation method of the photoelectric conversion device, the flexible perovskite photoelectric conversion device is obtained by sequentially preparing the flexible substrate, the transparent conductive electrode layer, the first charge transmission layer, the perovskite light absorption layer, the second charge transmission layer, the first electrode and the flexible packaging layer, the preparation process is simple, the flexibility of materials for preparing the flexible substrate and the flexible packaging layer is good, the size is small, and the inflammation reaction cannot be caused and the performance of an electric stimulation system cannot be influenced; on the basis of the photovoltaic effect principle, a perovskite flexible photoelectric conversion device with high response characteristic under weak light is prepared to wirelessly supply power for electronic devices such as a flexible stimulation electrode and the like, the problem of battery capacity is solved, and the battery does not need to be replaced through an operation; the prepared perovskite flexible photoelectric conversion device utilizes a wireless power supply technology of a photovoltaic effect principle, and has no electromagnetic compatibility problem on electronic devices in or around the body.
Drawings
Fig. 1 is a schematic structural view of a cross section of a photoelectric conversion device according to an embodiment of the present invention;
fig. 2 is a flowchart of a method for manufacturing a photoelectric conversion device according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of one configuration of a photoelectric conversion device having a single perovskite light absorbing layer in accordance with embodiments of the present invention;
FIG. 4 is a graph of the response characteristics of a photoelectric conversion device having a single perovskite light absorbing layer according to an embodiment of the present invention;
FIG. 5 is an output voltage characteristic diagram of a photoelectric conversion device according to an embodiment of the present invention under two conditions of no shielding of pigskin tissue and shielding of pigskin tissue;
FIG. 6 is a structural composition diagram of an integrally implanted flexible wireless electrical stimulation system according to an embodiment of the present invention;
fig. 7 is a block diagram of an example of an application of the integrally implanted flexible wireless electrical stimulation system of the embodiment of the invention under the skin of a stimulated subject;
FIG. 8 is a structural composition diagram of a flexible wireless electrical stimulation system with a non-implantable electrical stimulator, according to an embodiment of the present invention;
FIG. 9 is a block diagram of an exemplary use of a flexible wireless electrical stimulation system with a non-implantable electrical stimulator, according to embodiments of the present invention, under the skin of a subject being stimulated;
FIG. 10 is a schematic structural diagram of the implanted portion of a flexible wireless electrical stimulation system having a non-implantable electrical stimulator according to an embodiment of the present invention;
FIG. 11 is a structural composition diagram of a non-implantable flexible electrical stimulation system in accordance with embodiments of the present invention;
FIG. 12 is a diagram illustrating another configuration of a non-implantable flexible electrical stimulation system in accordance with embodiments of the present invention;
FIG. 13 is a schematic diagram of a configuration of degradable flexible stimulation electrodes and flexible extension leads according to an embodiment of the invention;
FIG. 14 is a molecular structure diagram of an adhesive gel composition for adhering a flexible stimulation electrode to a target tissue in accordance with embodiments of the present invention;
fig. 15 is a schematic diagram of the implementation process of polyglutamic acid to achieve high-strength adhesion of the flexible stimulation electrode and the tissue by using hydrogen bonds and covalent bonds according to the embodiment of the present invention.
Detailed Description
In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, but not all 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 application.
The terms "first," "second," "third," and "fourth," etc. in the description and claims of this application and in the accompanying drawings are used for distinguishing between different objects and not for describing a particular order. Furthermore, the terms "include" and "have," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
The embodiment of the invention provides a flexible perovskite photoelectric conversion device which consists of a flexible substrate, a transparent conductive electrode layer, a first charge transmission layer, a perovskite light absorption layer, a second charge transmission layer, a first electrode and a flexible packaging layer, wherein the flexible substrate and the flexible packaging layer are made of good materials and have good flexibility and small volume, and cannot cause inflammatory reaction and influence the performance of an electric stimulation system; on the basis of the photovoltaic effect principle, the perovskite flexible photoelectric conversion device with high response characteristic under weak light is used for wirelessly supplying power to electronic devices such as flexible stimulation electrodes, the problem of battery capacity is solved, and the batteries do not need to be replaced through an operation; the wireless power supply technology utilizing the photovoltaic effect principle has no electromagnetic compatibility problem on electronic devices in or around the body. The photoelectric conversion device provided by the embodiment of the invention can be applied to any scene needing power supply for electronic devices, such as implantable or non-implantable electric stimulation devices or systems.
As shown in fig. 1, an embodiment of the present invention proposes a photoelectric conversion device including:
a transparent conductive electrode layer 102;
a flexible substrate 101 disposed on one side of the transparent conductive electrode layer 102, the flexible substrate 101 being made of a biocompatible material having high transmittance for target light;
a first charge transport layer 103 disposed on a side of the transparent conductive electrode layer 102 away from the flexible substrate 101;
a perovskite light absorbing layer 104 disposed on a side of the first charge transport layer 103 remote from the transparent conductive electrode layer 102;
a second charge transport layer 105 disposed on the side of the perovskite light absorbing layer 104 remote from the first charge transport layer 103;
a first electrode 106 disposed on a side of the second charge transport layer 105 remote from the perovskite light absorbing layer 104;
a flexible packaging layer 107, wherein the flexible packaging layer 107 is made of a biocompatible material having high transmittance for target light. The flexible encapsulating layer 107 serves to protect the photoelectric conversion device. In one possible embodiment, the flexible encapsulation layer may directly encapsulate the structures of the flexible substrate 101, the transparent conductive electrode layer 102, the first charge transport layer 103, the perovskite light absorption layer 104, the second charge transport layer 105, and the first electrode 106, as shown in fig. 1. In another possible embodiment, the flexible encapsulation layer 107 may form a closed protective layer with the flexible substrate 101, which encapsulates or protects the transparent conductive electrode layer 102, the first charge transport layer 103, the perovskite light absorbing layer 104, the second charge transport layer 105, and the first electrode 106.
As shown in fig. 1, the photoelectric conversion device includes a flexible substrate 101, a transparent conductive electrode layer 102, a first charge transport layer 103, a perovskite light-absorbing layer 104, a second charge transport layer 105, a first electrode 106, and a flexible encapsulation layer 107, which are disposed from bottom to top.
The flexible substrate 101 is used for transmitting an incident target light (simply referred to as an incident light) 100. It is understood that, in order to realize the photoelectric conversion function, the flexible substrate 101 may be made of a flexible polymer material, for example, a biocompatible polymer such as polyethylene terephthalate (also called dacron) PET or polyethylene terephthalate PEN or polydimethylsiloxane PDMS. In order to reduce the overall volume of the optoelectronic device, in one possible embodiment the thickness of the flexible substrate is ≦ 300 μm. Alternatively, the target light (i.e., incident light 100) may be various artificial light sources from infrared LEDs, infrared quantum dot LEDs, infrared lasers, infrared thermal radiation, and the like; or a natural light source from sunlight.
The incident light 100 sequentially penetrates through the flexible substrate 101, the transparent conductive electrode layer 102 and the first charge transport layer 103 and then enters the perovskite light absorption layer 104, and the perovskite light absorption layer 104 absorbs the incident light 100 and generates holes and electrons as carriers based on the principle of photovoltaic effect. The carriers generated by the perovskite light absorbing layer 104 may move up or down: if the carriers move downwards, the carriers are collected by the transparent conductive electrode layer 102 after being transmitted by the first charge transmission layer 103; if the carriers move upward, the carriers are collected by the first electrode 105 after passing through the transport action of the second charge transport layer 105.
Specifically, the perovskite light absorption layer 104 may be made of a perovskite material having a high response characteristic to weak light. Alternatively, the thickness of the perovskite light absorbing layer 104 may be 50-2000 nanometers, the optical forbidden bandwidth of the perovskite light absorbing layer 104 may be 0.1-5.0 electron volts, and the light absorbing layer spectral response of the perovskite light absorbing layer 104 may range from 248 nanometers to 12400 nanometers. It is understood that, in addition to the structure of the single-layer perovskite light-absorbing layer 104, the embodiment of the invention may also adopt the structure of the multi-layer perovskite light-absorbing layer 104 to enhance the photoelectric conversion effect, thereby further enhancing the performance of the photoelectric conversion device.
The transparent conductive electrode layer 102 may be made of metal oxide such as indium-doped tin oxide ITO, an ultra-thin metal thin film (e.g., Au or Ag), a metal nano-grid (e.g., Au or Ag nano-grid), or a metal nano-wire (e.g., Au or Ag nano-wire). Illustratively, if the transparent conductive electrode layer is ITO, the thickness of the ITO can be 10-1000 nanometers and the resistivity can be 1-50 ohms per unit area.
It is understood that, corresponding to the type of carriers transported, if the carriers transported by the first charge transport layer 103 are holes, the first charge transport layer 103 is a hole transport layer; if the carriers transported by the first charge transport layer 103 are electrons, the first charge transport layer 103 is an electron transport layer. Alternatively, the first charge transport layer may be made of at least one material selected from Poly (3, 4-ethylenedioxythiophene) -Poly (styrenesulfonic acid) PEDOT: PSS, Poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] PTAA, Poly [ bis (4-phenyl) (4-butylphenyl) amine ] Poly-TPD, 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline TAPC, nickel oxide NiOx, or tin dioxide SnO 2.
It is understood that, corresponding to the type of carriers transported, if the carriers transported by the second charge transport layer 105 are holes, the second charge transport layer 105 is a hole transport layer; if the carriers transported by the second charge transport layer 105 are electrons, the second charge transport layer 105 is an electron transport layer. Alternatively, the second charge transport layer may be prepared using the first material and the second material; alternatively, the second charge transport layer may employ poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]PTAA or 2,2',7,7' -tetrakis [ N, N-di (4-methoxyphenyl) amino]At least one material of-9, 9' -spirobifluorene spiro-OMeTAD. Wherein the first material comprises C60PCBM or ICBA, the second material comprises BCP or SnO2Any one of the above. Alternatively, the corresponding thicknesses of C60, PCBM, ICBA, BCP, SnO2, PTAA, spiro-OMeTAD may be set to 5-80 nm, 10-90 nm, 10-150 nm, 2-20 nm, 5-50 nm, 20-300 nm, 5-300 nm, respectively.
In the embodiment of the present invention, the first electrode 106 may be made of a metal material such as silver Ag, gold Au, copper Cu, or other materials with conductive properties (e.g., conductive plastic, conductive rubber, etc.), and the thickness of the first electrode 106 may be 10 to 500 nm. For example, if the first electrode 106 is a metal electrode made of a metal material, such as a silver electrode, the thickness of the metal electrode may be 20-400 nm.
As the carriers accumulate, a relatively constant electric field may be formed between the first electrode 106 and the transparent conductive electrode layer 102, driving electrons or holes generated by the perovskite light absorbing layer 104 to move in the first charge transport layer 103 or the second charge transport layer 105. Illustratively, the first electrode 106 may collect electrons and the transparent conductive electrode layer 102 may collect holes, thereby forming a relatively constant electric field having the first electrode 106 as a negative electrode and the transparent conductive electrode layer 102 as a positive electrode, the direction of the electric field being directed from the transparent conductive electrode layer 102 to the first electrode 106.
And the flexible packaging layer 107 is mainly used for flexibly packaging the prepared photoelectric conversion device. In order to prevent the flexible photoelectric conversion device from being corroded by tissue fluid, the encapsulation material used for the flexible encapsulation layer 107 needs to have an insulating effect on the tissue fluid, and for example, a polydimethylsiloxane PDMS material or a Parylene/Parylene material may be used.
Based on the photoelectric conversion device of fig. 1, an embodiment of the present invention provides a method for manufacturing a photoelectric conversion device, as shown in fig. 2, the method including the following steps S201 to S206:
s201, preparing a transparent conductive electrode on a flexible substrate;
s202, preparing a first charge transport layer on the transparent conductive electrode;
s203, preparing a perovskite light absorption layer on the first charge transport layer;
s204, preparing a second charge transport layer on the perovskite light absorption layer;
s205, preparing a first electrode on the second charge transport layer;
s206, preparing a flexible packaging layer, wherein the flexible packaging layer is made of a biocompatible material with high transmittance on target light; the flexible packaging layer wraps the first electrode, the second charge transmission layer, the perovskite light absorption layer, the first charge transmission layer, the transparent conductive electrode layer and the flexible substrate; or the flexible packaging layer and the flexible substrate form a protective layer, and the protective layer wraps the first electrode, the second charge transmission layer, the perovskite light absorption layer, the first charge transmission layer and the transparent conductive electrode layer.
In step S201, the material used for the flexible substrate may be a flexible polymer material, for example, the material used for the flexible substrate may be a biocompatible polymer such as poly PET or PEN or PDMS. Optionally, the flexible substrate has a thickness ≦ 300 μm.
In step S201, a magnetron sputtering method or a thermal evaporation method may be used to prepare a transparent conductive electrode on a flexible substrate, and the electrode material of the transparent conductive electrode may be a metal oxide such as ITO, an ultrathin metal film (e.g., Au or Ag), a metal nano-grid (e.g., Au or Ag nano-grid), or a metal nanowire (e.g., Au or Ag nanowire). For example, when ITO is selected, the thickness of ITO is 10-1000 nm and the resistivity is 1-50 ohm/unit area.
In step S202 of the embodiment of the present invention, the transparent conductive electrode can be prepared by the following two methods:
the method comprises the following steps: depositing a cavity transport layer such as PEDOT, PSS, PTAA, Poly-TPD, TAPC, NiOx and the like on the transparent conductive electrode by adopting a spin coating method or a vacuum evaporation method to serve as a first charge transport layer, wherein the thickness of the cavity transport layer is 2-100 nanometers;
the second method comprises the following steps: and depositing a tin dioxide layer on the transparent conductive electrode by adopting a spin-coating method or an atomic layer deposition method, and annealing the tin dioxide layer at the temperature of 30-100 ℃ to obtain the annealed tin dioxide layer serving as a first charge transport layer, wherein the thickness of the tin dioxide layer is 2-100 nanometers.
The embodiment of the invention can provide two methods for the user to select according to the actual requirement, and is more flexible and convenient.
Alternatively, in step S203 of the embodiment of the present invention, the perovskite light absorption layer may be prepared by the following two methods:
the method comprises the following steps: preparing a perovskite light absorption layer on the first charge transmission layer by adopting a spin coating method, and annealing the perovskite light absorption layer at the temperature of 30-100 ℃, wherein the optical forbidden bandwidth of the perovskite light absorption layer is 0.1-5.0 electron volts, and the spectral response range of the perovskite light absorption layer is 248-12400 nanometers.
The second method comprises the following steps: preparing a perovskite light absorption layer on the first charge transport layer by adopting a vacuum deposition method; wherein the optical forbidden band width of the perovskite light absorption layer is 0.1-5.0 electron volt, and the spectral response range of the perovskite light absorption layer is 248-12400 nanometers.
And in the second method, a vacuum deposition method is adopted, so that the final perovskite light absorption layer can be prepared without annealing treatment.
Alternatively, in step S204 of the embodiment of the present invention, the second charge transport layer may be prepared by the following two methods:
the method comprises the following steps: depositing a first material and a second material on the surface of the perovskite light absorption layer to obtain a second charge transport layer, wherein the first material comprises any one of C60, PCBM and ICBA, and the second material comprises BCP or SnO2Any one of (a);
the second method comprises the following steps: and depositing at least one of poly-PTAA or spiro-OMeTAD on the surface of the perovskite light absorption layer by a solution method or a vacuum thermal evaporation method to obtain a second charge transport layer.
Alternatively, in step S205 of the embodiment of the present invention, the first electrode may be prepared by the following method:
and depositing a first electrode by using a vacuum thermal evaporation method, wherein the first electrode can be a metal electrode, such as gold, silver, copper or platinum-iridium alloy, and the thickness of the first electrode can be 50-500 nanometers.
Alternatively, in step S206 of the embodiment of the present invention, the flexible encapsulation layer may be prepared by the following method:
preparing a flexible encapsulation layer (as shown in 107 of fig. 1) on the outer surfaces of the flexible substrate, the transparent conductive electrode layer, the first charge transport layer, the perovskite light absorption layer and the second charge transport layer using a biocompatible material having high transmittance to a target light; or, a biocompatible material with high transmissivity to target light is adopted, and a flexible packaging layer is prepared on the outer surfaces of the transparent conductive electrode layer, the first charge transmission layer, the perovskite light absorption layer and the two charge transmission layers, so that a closed protective layer is formed by the flexible packaging layer and the flexible substrate.
In order to prevent the flexible photoelectric conversion device from being corroded by the tissue fluid, the encapsulation material used for the flexible encapsulation layer 107 needs to have an insulating effect on the tissue fluid, and for example, a PDMS material or a Parylene material may be used.
A flexible photoelectric conversion device having a single-layer perovskite light-absorbing layer is obtainable based on steps S201-S206. It will be appreciated by those skilled in the art that a similar process flow may be used to fabricate a flexible photoelectric conversion device having a multi-layered perovskite light absorbing layer, and a plurality of photoelectric conversion components in series or/and parallel with the flexible photoelectric conversion device.
A schematic structural diagram of a flexible photoelectric conversion device with a single-layer perovskite light-absorbing layer obtained based on steps S201-S206 is shown in fig. 3, and includes a flexible substrate 101, a perovskite light-absorbing layer 104, a transparent conductive electrode (not shown in fig. 3), positive and negative electrode contacts 1061 and 1062 from which a first electrode is led, and a flexible encapsulation layer 107. Alternatively, the thickness of the flexible photoelectric conversion device can be controlled to be less than or equal to 500 μm in order to save volume. The spectral response range of the flexible photoelectric conversion device can be 248-12400 nm. Illustratively, the spectral response range of the flexible photoelectric conversion device can be 300-1100nm, the output voltage is 0-0.81V, and the output current is 29.02mA/cm2As shown in fig. 4. In fig. 4, the abscissa is the Wavelength of the incident light in nm; EQE (shorthand for External Quantum Efficiency) is the External Quantum Efficiency in%; jsc (Shorthand for Short-circuit Current sensitivity) is Short-circuit Current in mA/cm2。
The flexible photoelectric conversion device in fig. 4 still has a high voltage response under weak light. To verify this, an experiment can be designed to cover the flexible perovskite photoelectric response device of fig. 4 with pig skin tissue containing a fat layer with a certain thickness under the radiation intensity of standard sunlight, and the obtained experimental result is shown in fig. 5. As can be seen from fig. 5, the flexible perovskite photoresponsive device has a response voltage of about 0.65 volts even though the pigskin blocks visible light in sunlight, thereby enabling wireless power supply to the electrostimulation device or system. Further, the embodiment of the invention can also adopt a mode of connecting a plurality of perovskite light absorption layers or a plurality of photoelectric conversion devices in series and in parallel, so as to provide electric energy with enough voltage and current intensity for the flexible wireless electric stimulation device or system.
Based on the foregoing description, an embodiment of the present invention further provides an apparatus (referred to as a power supply apparatus for short) capable of supplying power to an electrical stimulation apparatus or system, where the power supply apparatus includes:
and the photoelectric conversion device is used for supplying power to the flexible stimulation electrode of the electrical stimulation device or system. The photoelectric conversion device is prepared by the method of the previous preparation method embodiment.
Optionally, the device may further comprise a flexible energy storage device, and the flexible energy storage device may be a flexible solid-state lithium ion battery, a flexible supercapacitor, a flexible graphene/graphene battery, or a stretchable flexible battery, or the like. Similar to the flexible substrate and the flexible encapsulation layer, the flexible energy storage device may also be encapsulated by a flexible biocompatible material such as PDMS, Parylene, etc. Optionally, the thickness of the flexible energy storage device is less than or equal to 2 mm. It is understood that, in order to reduce the volume of the device, the photoelectric conversion device and the flexible energy storage device can be integrated into an integrated flexible wireless power supply device.
The embodiment of the invention is additionally provided with the flexible energy storage device, so that the device can store certain energy, can still continuously provide energy for the electrical stimulation device or system under the condition of no external illumination, and is more reliable.
Based on the foregoing description, embodiments of the present invention also provide a system for performing electrical stimulation, the system including:
the photoelectric conversion device is used for receiving and converting the target light into electric energy;
and the flexible stimulation electrode is connected with the photoelectric conversion device and used for generating an electrical stimulation signal under the action of the electric energy.
In the embodiment of the present invention, the photoelectric conversion device is manufactured by the method in the foregoing manufacturing method embodiment.
It will be appreciated that the flexible stimulation electrodes may be in contact with the target tissue to which stimulation is to be applied. Similar to the flexible substrate and flexible encapsulation layer, the flexible stimulation electrode may also be encapsulated by a flexible biocompatible material such as PDMS, etc. Optionally, the thickness of the flexible stimulation electrode is less than or equal to 0.9 mm.
Further, the system for performing electrical stimulation may further comprise at least one of:
the electrical stimulator is used for generating target light sent to the photoelectric conversion device or generating an electrical stimulation signal sent to the flexible stimulation electrode;
the flexible energy storage device is used for storing electric energy generated by the photoelectric conversion device and supplying power to the flexible stimulation electrode;
and the flexible extension lead is used for connecting the photoelectric conversion device and the flexible stimulation electrode or connecting the electric stimulator and the flexible stimulation electrode.
In the embodiment of the present invention, the flexible energy storage device may be the flexible energy storage device described in the foregoing embodiment of the power supply apparatus, and details thereof are not repeated herein.
Specifically, the electrical stimulator may include a processor, a stimulation parameter controller, and a pulse generator: the processor is used for processing signals or data, the stimulation parameter controller is used for controlling stimulation parameters such as current magnitude, and the pulse generator is used for generating pulse signals. The electric stimulator can also be prepared on the flexible substrate, so that a flexible electric stimulation module is obtained. Depending on the application, the electric stimulator may be used as a driving source of the target light emitter to drive the target light emitter to emit the target light such as the infrared light (in this case, the electric stimulator is connected to the target light emitter); the electric stimulator can also be used as a controller of the flexible stimulation electrode, and the pulse, the frequency, the intensity and the like of the electric stimulation of the flexible stimulation electrode are controlled under the electric energy driving action of the photoelectric conversion device or the energy storage and power supply device (at this moment, the electric stimulator is connected with the flexible power supply device and the flexible stimulation electrode). The flexible power supply device may comprise the aforementioned photoelectric conversion device or/and the aforementioned flexible energy storage device. When used as a controller for a flexible stimulation electrode, the electrical stimulator may further comprise a voltage regulation module for regulating the voltage provided by the photoelectric conversion device and/or the flexible energy storage device as described above to a clinically desirable voltage.
The flexible extension lead is a lead for transmitting signals or data. Similar to the flexible substrate and flexible encapsulation layer, the flexible extension wires may be encased by a flexible biocompatible material such as PDMS or the like.
Alternatively, the electrode contacts of the flexible stimulation electrode and the conductive material inside the flexible extension lead may be prepared from a flexible conductive polymer or an ion conductive gel.
Based on the foregoing system embodiments, clinically applicable electrical stimulation systems are available. The electrical stimulation system encompasses three exemplary embodiments of electrical stimulation protocols: an integrally implanted flexible radio-stimulation system, a flexible radio-stimulation system with a non-implanted electrical stimulator, and a non-implanted flexible radio-stimulation system.
In one possible implementation, an integrally implanted flexible radio-stimulation system is provided, which is implanted inside (i.e. in the body) the target tissue to be stimulated, and mainly comprises a flexible power supply and a flexible stimulation electrode, as shown in fig. 6. The integrally implanted flexible wireless electrical stimulation system can also comprise the electrical stimulator in the embodiment of the system, and the electrical stimulator is used for controlling the pulse, frequency, intensity and the like of electrical stimulation. The flexible power supply may be the power supply of the previous device embodiments, including a photoelectric conversion device having a high response characteristic in low light conditions. In one embodiment, the flexible power supply may further comprise a flexible energy storage device as described in the previous embodiments of the device. In the flexible wireless electric stimulation system, a flexible stimulation electrode is in contact with target tissue to be stimulated, and the flexible electrode can be connected with a flexible power supply device or the electric stimulator through a flexible extension lead.
Fig. 7 shows an example of the use of an integrally implanted flexible wireless electrical stimulation system under the skin 700 of a subject to be stimulated. In fig. 7, 701 is a light source for emitting a target light ray (e.g., infrared ray) having high transmittance to a tissue such as skin, connective tissue, fat, etc. as the incident light 100. The target light can come from various artificial light sources such as infrared LEDs, infrared quantum dot LEDs, infrared heat radiation and the like or infrared lasers; in another embodiment, the target light may also be a natural source of light from sunlight.
In fig. 7, the flexible power supply apparatus may include a photoelectric conversion device 702 and a flexible energy storage device 703. The flexible power supply may be implanted under the skin, for example between the skin and the subcutaneous connective tissue or adipose layer. The photoelectric conversion device 702 may be implanted within 25mm of the skin, receiving the incident light 100 and converting it into electrical energy. The electrical stimulator 704 controls parameters such as stimulation frequency, pulse and intensity of the flexible electrode 706 through the flexible extension lead 705 under the action of the electrical energy of the flexible power supply. The flexible power supply may be integrated with the electrical stimulator 704 as an integrated power and stimulation module. Optionally, the thickness of the integrated power supply and stimulation module can be less than or equal to 5mm, the length/width of the integrated power supply and stimulation module can be less than or equal to 50mm, and the implantation depth of the integrated power supply and stimulation module can be within 25mm subcutaneously. The integrated module can provide pulse electrical stimulation with the voltage of 0.01V-500V and the current of 0.01-500mA to the flexible stimulation electrode 706 under the driving of the wireless power supply module, the stimulation frequency is controlled by a pulse generator of the electrical stimulator 704, and the stimulation frequency is adjustable within the range of 0-10 kHz.
In another possible implementation, a flexible wireless electrical stimulation system with a non-implanted electrical stimulator may be provided, which, unlike the integrally implanted flexible wireless electrical stimulation system of fig. 6, may be located outside the body to constitute a non-implanted external electrical stimulator, as shown in fig. 8. Unlike the flexible wireless electrical stimulation system of fig. 6, the electrical stimulator is connected to and controls a light source (e.g., an infrared emitter, etc.).
Fig. 9 shows an example of the use of a flexible wireless electrical stimulation system with a non-implantable electrical stimulator under the skin 700 of a subject to be stimulated. In fig. 9, 901 is a power supply, 902 is a non-implanted electrical stimulator, 903 is a light source (e.g., an infrared emitter, etc.), 100 is target light (i.e., incident light), 904 is a photoelectric conversion device, 905 is a flexible extension wire, 906 is a flexible stimulation electrode, and 907 is target tissue.
In fig. 9, under the driving of an external power source 901, a non-implantable external electrical stimulator 902 is connected to and controls a light source (e.g., an infrared emitter) to emit a target light with a certain frequency and intensity as an incident light 100. In this embodiment, the implantable flexible power supply may comprise only the photoelectric conversion device 904 described previously; the photo-conversion device 904 is directly connected to the flexible stimulation electrode by a flexible extension lead 905. The photoelectric conversion device 904 converts the received incident light 100 into an electrical stimulation signal of the same frequency. In one possible embodiment, the non-implantable external electrical stimulator may be powered by a photovoltaic cell and/or a capacity of energy storage device (e.g., a supercapacitor, etc.).
Figure 10 illustrates one embodiment of a flexible wireless electrical stimulation system with a non-implantable electrical stimulator. The implanted part of the flexible wireless electric stimulation system comprises a flexible photoelectric conversion device 1001, a flexible extension lead 1002 and a flexible stimulation electrode 1003. Flexible extension leads 1002 connect the positive and negative electrodes of the flexible photoelectric conversion device 1001 to the contacts of the flexible stimulation electrode 1003. The elastic modulus of the flexible stimulation electrode 1003 can be matched with that of the target tissue, so as to avoid damage to the target tissue caused by mismatching of the elastic modulus; the flexible extension lead 1002 may have a modulus of elasticity that is more than 5% lower than the modulus of elasticity of the surrounding tissue, thereby avoiding restriction and interference of the flexible extension lead with movement of the tissue at the implantation site. The flexible photoelectric conversion device can adopt the photoelectric conversion device, has a biocompatible coating with high transmissivity to target light, and has a thickness of less than or equal to 1mm and a length, a width and other dimensions of less than or equal to 50 mm. When the flexible electrical stimulation system shown in fig. 10 is used, the flexible photoelectric conversion device is implanted within 25mm of the skin, the flexible stimulation electrode acts on target tissues (muscles, nerves and the like), and the length of the flexible extension lead is determined by the implantation depth of the stimulation electrode.
In one possible implementation, the electrical stimulator, the flexible power supply and the flexible stimulation electrodes are all located outside the body, constituting a non-implantable flexible radio stimulation system for transcutaneous electrical stimulation of the target tissue, as shown in fig. 11. In the non-implanted flexible electrical stimulation system, the flexible power supply device is the photoelectric conversion device; the flexible power supply device and the flexible stimulation electrode can also be integrated into an integrated flexible wireless stimulation electrode. In one embodiment, the flexible wireless stimulation electrode may include other circuit modules (e.g., amplifiers, filters, etc.) for amplifying the output voltage of the flexible photoelectric conversion device to a clinically required stimulation voltage. When the non-implanted flexible wireless electric stimulation system is used, the flexible wireless stimulation electrode can be adhered to the surface of target skin, the electric stimulator is connected with and controls the light source to emit target light with certain intensity and frequency as incident light, the flexible photoelectric conversion device converts the received incident light into an electric signal and acts on the target skin through the flexible stimulation electrode, and wireless stimulation on the target skin is achieved.
In another possible embodiment, the flexible power supply, the electrical stimulator and the flexible stimulation electrode may be integrated into an integrated, non-implantable, flexible wireless electrical stimulation system for transcutaneous electrical stimulation of a target tissue, as shown in fig. 12, wherein the flexible power supply, the electrical stimulator and the flexible stimulation electrode are all located outside the body. In the non-implantable flexible electrical stimulation system in fig. 12, the flexible power supply device is an integrated flexible power supply device composed of the photoelectric conversion device and the flexible energy storage device as described above. The electrical stimulator is the electrical stimulator which controls the pulse, frequency, intensity and the like of electrical stimulation under the action of electric energy in the previous system embodiment, and the flexible stimulation electrode is the flexible stimulation electrode in the previous embodiment. When the non-implanted flexible wireless electric stimulation system is used, the flexible stimulation electrode can be adhered to the surface of target skin, the light source emits target light with certain intensity and frequency as incident light, the flexible photoelectric conversion device converts the received incident light into an electric signal (namely electric energy), the electric stimulator controls the pulse, the frequency, the intensity and the like of the electric stimulation of the flexible stimulation electrode under the action of the electric energy of the flexible photoelectric conversion device, and the electric stimulation is acted on the target skin through the flexible stimulation electrode to realize the radio stimulation of the target skin.
In the various embodiments described above, the flexible radio stimulation system may be used for muscle stimulation, peripheral nerve stimulation, spinal nerve stimulation, cortical stimulation, deep brain electrical stimulation, and the like. Illustratively, the flexible electrical stimulation system for leg peripheral nerve stimulation can be used for stimulating drop foot after cerebral stroke and also can be used for electrically stimulating nerve recovery after injuries such as nerve compression or transverse injury; the flexible stimulation electrode is wrapped and fixed on the target nerve, the flexible photoelectric conversion device converts the received light into an electrical stimulation signal, and the electrical stimulation signal is conducted to the stimulation electrode through the extension lead to apply electrical stimulation to the target nerve.
In an implantable flexible electrical stimulation system, the flexible stimulation electrodes and flexible extension leads may also be made of biocompatible and biodegradable materials that degrade after a period of implantation in the body. Specifically, in the integrally implanted flexible wireless electric stimulation system, after the flexible extension lead is degraded, the power supply device and the electric stimulator implanted under the skin can be taken out through a minimally invasive incision of the skin; in the flexible electric stimulation system containing the non-implantable external electric stimulator, after the flexible extension lead is degraded, the flexible photoelectric conversion device implanted under the skin can be taken out through a minimally invasive incision of the skin.
Figure 13 shows an example of the structure of a degradable flexible stimulation electrode and a flexible extension wire. The flexible stimulation electrode and the extension lead mainly comprise an electrode contact 1206, a connecting lead 1203 for connecting the flexible power supply device/electric stimulator 1202 and the electrode contact 1206, an insulating layer 1204 for the electrode contact 1206/connecting lead 1203, a base body (comprising an upper base 1205 and a lower base 1201) and the like. In one embodiment, an isolation layer 1207 of a material that further isolates the substrate is provided around the electrode contacts 1206. The electrode contacts 1206 and the connecting wires 1203 may be a degradable biocompatible metal film (such as magnesium, molybdenum, and alloys thereof), a degradable conductive polymer composite material (such as a composite conductive material composed of degradable materials such as polyethylene dioxythiophene PEDOT and polycaprolactone-polyglutamic acid PCL/PGA), or a composite material of graphene and derivatives thereof (such as a composite conductive material composed of reduced graphene oxide and polycaprolactone PCL). The electrode contacts 1206 and the biodegradable insulating polymer around the connecting wires, such as polycaprolactone PCL or poly-4-methyl-epsilon-caprolactone PMCL.
To address the difficulty of securing the flexible stimulation electrode to the target tissue, in one embodiment, the base of the flexible stimulation electrode of FIG. 13 is comprised of a biodegradable wet tissue adhesive gel material. The wet tissue adhesive gel is capable of forming hydrogen bonds, covalent bonds, etc. with the biological tissue to adhere to the biological tissue without suturing and to avoid interfacial slippage. In one embodiment, the main component of the wet tissue adhesive gel may be PGA-NHS ester polyglutamic acid with N-hydroxysuccinimide NHS ester group, the molecular structure of which is shown in FIG. 14; in one embodiment, the matrix material may be prepared by mixing and crosslinking PGA-NHS ester and other biocompatible polymer materials (such as sodium alginate, chitin, etc.). When the flexible stimulation electrode containing the PGA-NHS ester is contacted with target tissues in vivo, hydrogen bonds can be formed with the tissues, and rapid adhesion is realized. Further, the active ester group on PGA-NHS ester is able to form a covalent bond with amino-NH 2 on the tissue surface, thereby achieving high strength of tissue adhesion, as shown in fig. 15. The wet tissue adhesive gel material of fig. 15 may be used in a variety of applications where adhesion to wet tissue is desired.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
1. A photoelectric conversion device, characterized by comprising:
a transparent conductive electrode layer;
a flexible substrate disposed on one side of the transparent conductive electrode layer;
a first charge transport layer disposed on a side of the transparent conductive electrode layer away from the flexible substrate;
the perovskite light absorption layer is arranged on one side, far away from the transparent conductive electrode layer, of the first charge transmission layer;
a second charge transport layer disposed on a side of the perovskite light absorbing layer distal from the first charge transport layer;
a first electrode disposed on a side of the second charge transport layer distal from the perovskite light absorbing layer;
the flexible packaging layer is made of a biocompatible material with high transmittance on target light;
the flexible encapsulation layer encapsulates the first electrode, the second charge transport layer, the perovskite light absorption layer, the first charge transport layer, the transparent conductive electrode layer, and the flexible substrate; or the flexible packaging layer and the flexible substrate form a protective layer, and the first electrode, the second charge transmission layer, the perovskite light absorption layer, the first charge transmission layer and the transparent conductive electrode layer are wrapped by the protective layer.
2. The photoelectric conversion device according to claim 1, wherein the first charge transport layer is formed using at least one material selected from the group consisting of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly [ bis (4-phenyl) (4-butylphenyl) amine ], 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline, nickel oxide, and tin dioxide;
the second charge transport layer is prepared from a first material and a second material, the first material comprises fullerene, [6, 6] -phenyl-C61-isopropyl butyrate or any one of 56,60:2,3] [5,6] fullerene-C60-IH, and the second material comprises any one of 2, 9-dimethyl-4, 7 diphenyl-1, 10-phenanthroline or tin dioxide; or the second charge transport layer is prepared by adopting at least one material of poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] or 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene.
3. The photoelectric conversion device as claimed in claim 1, wherein the thickness of the perovskite light absorption layer is 250-2000 nm, the optical forbidden bandwidth of the perovskite light absorption layer is 0.1-5.0 ev, and the spectral response range of the perovskite light absorption layer is 248-12400 nm.
4. A method for manufacturing a photoelectric conversion device, the method comprising:
preparing a transparent conductive electrode on a flexible substrate;
preparing a first charge transport layer on the transparent conductive electrode;
preparing a perovskite light absorption layer on the first charge transport layer;
preparing a second charge transport layer on the perovskite light absorption layer;
preparing a first electrode on the second charge transport layer;
preparing a flexible packaging layer, wherein the flexible packaging layer is made of a biocompatible material with high transmittance on target light;
the flexible encapsulation layer encapsulates the first electrode, the second charge transport layer, the perovskite light absorption layer, the first charge transport layer, the transparent conductive electrode layer, and the flexible substrate; or the flexible packaging layer and the flexible substrate form a protective layer, and the first electrode, the second charge transmission layer, the perovskite light absorption layer, the first charge transmission layer and the transparent conductive electrode layer are wrapped by the protective layer.
5. The method for manufacturing a photoelectric conversion device according to claim 4, wherein the manufacturing of the first charge transport layer on the transparent conductive electrode comprises:
depositing at least one material selected from (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly [ bis (4-phenyl) (4-butylphenyl) amine ], 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline, or nickel oxide on the transparent conductive electrode by using a spin coating method or a vacuum evaporation method to obtain a hole transport layer as a first charge transport layer, wherein the thickness of the hole transport layer is 2-100 nm;
or depositing a tin dioxide layer on the transparent conductive electrode by adopting a spin coating method or an atomic layer deposition method, and annealing the tin dioxide layer at 30-100 ℃ to obtain the annealed tin dioxide layer serving as a first charge transport layer, wherein the thickness of the tin dioxide layer is 2-100 nanometers.
6. The method for producing a photoelectric conversion device according to claim 4, wherein the production of the perovskite light-absorbing layer on the first charge transport layer comprises:
preparing a perovskite light absorption layer on the first charge transmission layer by adopting a spin coating method, and annealing the perovskite light absorption layer at the temperature of 30-100 ℃;
or preparing a perovskite light absorption layer on the first charge transmission layer by adopting a vacuum deposition method;
wherein the optical forbidden band width of the perovskite light absorption layer is 0.1-5.0 electron volt, and the spectral response range of the perovskite light absorption layer is 248-12400 nanometers.
7. The method for producing a photoelectric conversion device according to claim 4, wherein the producing a second charge transport layer on the perovskite light absorption layer comprises:
depositing a first material and a second material on the surface of the perovskite light absorption layer to obtain a second charge transport layer, wherein the first material comprises any one of fullerene, [6, 6] -phenyl-C61-butyric acid isopropyl ester or 56,60:2,3] [5,6] fullerene-C60-IH, and the second material comprises any one of 2, 9-dimethyl-4, 7 diphenyl-1, 10-phenanthroline or tin dioxide;
or, depositing at least one material of poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] or 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene on the surface of the perovskite light absorption layer by adopting a solution method or a vacuum thermal evaporation method to obtain the second charge transport layer.
8. An apparatus, characterized in that the apparatus comprises:
a photoelectric conversion device according to any of claims 1 to 3, for powering a flexible stimulation electrode.
9. A system, characterized in that the system comprises:
the photoelectric conversion device according to any one of claims 1 to 3, for receiving and converting a target light into an electric energy;
and the flexible stimulation electrode is connected with the photoelectric conversion device and used for generating an electrical stimulation signal under the action of the electric energy.
10. The system of claim 9, further comprising at least one of:
the electric stimulator is used for controlling the light source to generate the target light transmitted to the photoelectric conversion device or generating the electric stimulation signal transmitted to the flexible stimulation electrode;
the flexible energy storage device is used for storing the electric energy generated by the photoelectric conversion device and supplying power to the flexible stimulation electrode;
and the flexible extension lead is used for connecting the photoelectric conversion device and the flexible stimulation electrode or connecting the electric stimulator and the flexible stimulation electrode.
11. The system of claim 10, wherein the system is any one of an entirely implantable flexible radio stimulation system or a flexible radio stimulation system with a non-implantable electrical stimulator or a flexible radio stimulation system with a non-implantable flexible stimulation electrode.
12. The system of claim 11, wherein when the system is an integrally implanted flexible wireless electrical stimulation system, the optoelectronic conversion device is an implanted optoelectronic conversion device, the flexible stimulation electrode is an implanted flexible stimulation electrode, and the electrical stimulator is an implanted electrical stimulator for generating the electrical stimulation signal to the flexible stimulation electrode under the action of the electrical energy.
13. The system of claim 11, wherein when the system is a flexible wireless electrical stimulation system with a non-implantable electrical stimulator, the optoelectronic conversion device is an implantable optoelectronic conversion device, the flexible stimulation electrode is an implantable flexible stimulation electrode, and the electrical stimulator is a non-implantable electrical stimulator for controlling a light source to generate the target light to be sent to the optoelectronic conversion device.
14. The system of claim 11, wherein when the system is a flexible wireless electrical stimulation system having a non-implantable flexible stimulation electrode, the optoelectronic conversion device is a non-implantable optoelectronic conversion device, the flexible stimulation electrode is a non-implantable flexible stimulation electrode, and the electrical stimulator is a non-implantable electrical stimulator for controlling a light source to generate the target light to be sent to the optoelectronic conversion device.
15. The system of claim 12 or 13, wherein the base material in the implantable flexible stimulation electrode and/or the flexible extension lead is a wet tissue adhesive gel; alternatively, the implantable flexible stimulation electrode and the flexible extension lead are made of biocompatible and biodegradable materials.
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| CN113456433A (en) * | 2021-08-13 | 2021-10-01 | 北京大学人民医院 | Electric signal collector and human-computer interaction interface type exoskeleton rehabilitation system |
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