CN111599827A - Novel perovskite semiconductor type X-ray detector and preparation method thereof - Google Patents
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Abstract
The invention provides a perovskite semiconductor type X-ray detector which comprises a top electrode, a perovskite light absorption layer and a signal reading thin film transistor array, and further comprises a first interface layer and a second interface layer, wherein the first interface layer is positioned between the top electrode and the perovskite light absorption layer, and the second interface layer is positioned between the perovskite light absorption layer and the signal reading thin film transistor array. The invention also provides a preparation method of the perovskite semiconductor type X-ray detector. The perovskite semiconductor type X-ray detector is provided with the first interface layer and the second interface layer, so that the effective contact and adhesion between the perovskite light absorption layer and the top electrode as well as between the perovskite light absorption layer and the signal reading thin film transistor array are improved, the signal-to-noise ratio of the detector is improved, the response speed of the detector is improved, and the long-term stability of the performance of the perovskite detector is ensured.
Description
Technical Field
The invention belongs to the technical field of X-ray detectors, and particularly relates to a novel perovskite semiconductor type X-ray detector and a preparation method thereof.
Background
An X-ray detector is a type of device that receives X-ray radiation and converts the X-ray energy into electrical signals that can be recorded. The X-ray detector has the characteristics of higher spatial resolution, no detection damage and the like, can realize accurate detection of the internal fine structure of samples such as organisms, minerals, metals and the like, and is widely applied to the fields of medical treatment, security inspection, scientific research, nuclear industry, military industry and the like. According to the electrical signal conversion method of the X-ray detector, the X-ray detector is generally divided into a semiconductor type direct detector (which directly converts X-rays into electrical signals) and a scintillator type indirect detector (which converts X-rays into optical signals and then converts the optical signals into electrical signals through photoelectric detector accessories). The semiconductor type detector has higher imaging resolution and dynamic imaging capability than the scintillator type detector, so the semiconductor type detector has a larger application prospect. The existing semiconductor type X-ray detector comprises several parts, such as an electrode, a light absorption layer, and a signal readout thin film transistor array. The light absorption layer generates photo-generated electron and hole pairs by absorbing X-rays and generates directional photocurrent under the action of an external bias voltage, and the light absorption layer is the most critical part in the detector. Conventional light absorbing layer materials include single crystal silicon, polycrystalline selenium, and cadmium telluride materials, among others. In recent years, perovskite materials have attracted much attention due to their outstanding photoelectric properties and low production costs, and are considered as revolutionary light-absorbing layer materials.
At present, a perovskite semiconductor type X-ray detector mainly uses bulk perovskite single crystals as semiconductor light absorption layer materials, and the perovskite materials are in direct contact with a top electrode and also in direct contact with a signal readout thin film transistor array. This detector configuration has several drawbacks. First, the perovskite material is prone to becoming detached from or in poor contact with the top electrode and the signal readout thin film transistor array, resulting in either failure or limited transmission of the current signal, making it difficult to form an effective detection signal. Secondly, the detector needs to have as low noise as possible while ensuring as high a photocurrent as possible is output, the noise being related to the dark current level of the detector, which is essentially determined by the resistivity of the perovskite material itself. However, many perovskite materials have low self-resistivity, which results in huge dark current and annihilation of signals, and the perovskite materials themselves generate strong ion migration phenomenon under an electric field, which results in that dark current cannot be kept stable for a long time, and these factors result in low or unstable signal-to-noise ratio. Thirdly, the upper and lower surfaces of the perovskite material often have a large number of surface defects, and a serious ion migration phenomenon can be generated under the condition of an external electric field, so that the dark current cannot be kept stable for a long time, and the response speed of the detector is influenced. Finally, the perovskite material is in direct contact with the signal reading thin film transistor array and the top electrode of the detector, and is easy to chemically react with metal materials of the signal reading thin film transistor array and the top electrode, so that the performance of the perovskite light absorption layer is reduced, and the stability of the performance of the detector is influenced.
Disclosure of Invention
The invention aims to overcome the defects of the conventional perovskite semiconductor X-ray detector, provides a novel perovskite semiconductor X-ray detector and a preparation method thereof, and improves the multi-aspect performance of the perovskite semiconductor X-ray detector.
Accordingly, in a first aspect, the present invention provides a perovskite semiconductor type X-ray detector comprising a top electrode, a perovskite light absorbing layer and a signal readout thin film transistor array, further comprising a first interface layer and a second interface layer, the first interface layer being located between the top electrode and the perovskite light absorbing layer, the second interface layer being located between the perovskite light absorbing layer and the signal readout thin film transistor array.
Further, the materials of the first interface layer and the second interface layer are independently one or a combination of two or more of an organic material, an inorganic material, and a perovskite material, provided that the perovskite material of the first interface layer and the second interface layer is a different perovskite material than the perovskite material of the perovskite light absorbing layer.
In a specific embodiment, the material of the first interface layer is an organic material and the material of the second interface layer is also an organic material. In another specific embodiment, the material of the first interface layer is an organic material and the material of the second interface layer is an inorganic material. In yet another specific embodiment, the material of the first interface layer is an inorganic material and the material of the second interface layer is an organic material. In yet another specific embodiment, the material of the first interface layer is an inorganic material and the material of the second interface layer is also an inorganic material.
In further embodiments, the materials of the first interface layer, the perovskite light absorbing layer and the second interface layer are all perovskite materials, but the perovskite materials of the first interface layer and the second interface layer are of different perovskite materials than the perovskite materials of the perovskite light absorbing layer. In a particular embodiment, the perovskite material of the first interface layer and the second interface layer is the same perovskite material, and the perovskite material of the perovskite light absorbing layer is another perovskite material. In another specific embodiment, the perovskite material of the first interface layer is a first perovskite material, the perovskite material of the second interface layer is a second perovskite material, and the perovskite material of the perovskite light absorption layer is a third perovskite material.
It should be noted that the interface layer material of the present invention may use a combination of two or more of an organic material, an inorganic material, or a perovskite material, for example, a perovskite material in combination with an organic material or an inorganic material, or a perovskite material in combination with an organic material and an inorganic material, in addition to the organic material, the inorganic material, or the perovskite material alone.
Further, the organic material used as the interface layer material in the present invention is an organic polymer or an organic small molecule compound. Preferably, the organic material used as interface layer material is polyimide, carbon 60, Polymethylmethacrylate (PMMA), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA) or [6, 6] -phenyl-C61-methyl butyrate (PCBM).
Further, the inorganic material used as the interface layer material in the present invention is a metal oxide, a metal sulfide, a metal simple substance, or a carbon material. Preferably, the inorganic material used as the interface layer material includes, but is not limited to, titanium oxide, tin oxide, nickel oxide, aluminum oxide, zirconium sulfide, bismuth metal, graphite, or carbon black.
Further, the perovskite material used in the present invention is an inorganic perovskite material or an organic-inorganic hybrid perovskite material. Preferred inorganic perovskite materials include, but are not limited to, CsPbX3And CsSnX3Wherein X is one or more of I, Br and CI. Preferred organic-inorganic hybrid perovskite materials include, but are not limited to, CH3NH3PbI3、CH3NH3PbCl3、CH3NH3PbBr3、CH3CH2NH3PbCl3、CH3CH2NH3PbBr3、CH3CH2NH3PbI3、NH2CH＝NH2PbCl3、NH2CH＝NH2PbBr3And NH2CH＝NH2PbI3。
It is noted that the term "inorganic perovskite material" or "organic-inorganic hybrid perovskite material" as used herein refers to two different classes of perovskite materials, whereas the term "different perovskite materials" as used herein refers to perovskite materials of different structural formulae. Thus, for example, CsPbX3And CsSnX3All belong to inorganic perovskite materials, but they have different structural formulas, contain different composition elements and are different perovskite materials. Similarly, the various preferred organic-inorganic hybrid perovskite materials described above are different perovskite materials from each other. It is evident that one inorganic perovskite material is a different perovskite material than one organic-inorganic hybrid perovskite material.
Typically, the top electrode has a thickness of 10-60 μm, the first interface layer has a thickness of 1-10 μm, the second interface layer has a thickness of 1-10 μm, and the perovskite layer has a thickness of 10 μm-10 cm.
In a second aspect, the present invention provides a method of producing the perovskite semiconductor type X-ray detector of the first aspect of the present invention. The method comprises the following steps: preparing the second interface layer on the signal reading thin film transistor array, preparing the perovskite light absorption layer on the second interface layer, preparing the first interface layer on the perovskite light absorption layer, preparing the top electrode on the first interface layer, and finally preparing the perovskite semiconductor type X-ray detector.
The second interface layer is formed on the signal readout thin film transistor array, and the first interface layer is formed on the perovskite light absorption layer by using an evaporation method, a spin coating method, a spraying method or a blade coating method.
The perovskite light absorption layer on the second interface layer can be prepared by a spin coating method, a blade coating method, a spraying method or a single crystal growth method.
The top electrode on the first interface layer can be prepared by a blade coating method, a spraying method, an evaporation method or a magnetron sputtering method.
The invention has the beneficial effects that:
according to the perovskite semiconductor type X-ray detector, the first interface layer is arranged between the perovskite light absorption layer and the top electrode, so that the direct contact between the perovskite light absorption layer and the top electrode is avoided, the second interface layer is arranged between the perovskite light absorption layer and the signal reading thin film transistor array, the direct contact between the perovskite light absorption layer and the signal reading thin film transistor array is avoided, and the defects caused by the direct contact of the traditional perovskite semiconductor type X-ray detector are overcome. The first interface layer and the second interface layer can play multiple roles, so that the performance of the detector is improved, and the main roles are as follows:
(1) realize effective contact and adhesion
The interface layer can be used as a connecting layer, and is beneficial to effective contact and adhesion promotion of the perovskite light absorption layer and the top electrode as well as the signal reading thin film transistor array. Without the interface layer, the perovskite light absorption layer is easy to separate from the top electrode and the signal reading thin film transistor array or has poor contact, so that current signals cannot be transmitted or are limited in transmission, and effective detection signals are difficult to form.
(2) Improving signal-to-noise ratio of detector
The detector needs to have as low noise as possible while ensuring that as high a photocurrent as possible is output, and the noise is related to the dark current level of the detector. In the case of a detector without an interface layer, the dark current of the detector is substantially determined by the resistivity of the perovskite material itself. However, many perovskite materials have low self-resistivity, so that dark current is huge and signals are annihilated. And the appropriate interface layer has larger resistance, so that the dark current level of the detector can be reduced, and the noise of the detector is reduced. In addition, the appropriate interface layer can realize unidirectional conduction of electrons or holes (rectification effect) or other special surface effects through energy band adjustment, so that the switching ratio (photocurrent/dark current) of the detector is effectively improved. And many interface layers have tunneling effect, and the ratio of the detector photocurrent to the dark current can be greatly increased under specific conditions. These all greatly enhance the signal-to-noise ratio of the perovskite detector.
(3) Reduce current drift and improve response speed
Under the condition that the detector has no interface layer, the upper surface and the lower surface of the perovskite material often have a large number of surface defects, and a serious ion migration phenomenon can be generated under the condition of an external electric field, so that the dark current cannot be kept stable for a long time. The appropriate interface layer can well passivate the defects on the surface of the perovskite, and effectively inhibit the ion migration at the interface of the perovskite material, so that the current drift is reduced, and the response speed of the detector is improved.
(4) Ensure the long-term stability of the performance of the perovskite detector
In the absence of an interface layer for the perovskite detector, the perovskite material is in direct contact with the detector and the top electrode and with the signal readout thin film transistor array. The top electrode and the signal readout thin film transistor array comprise metal materials, and some perovskites are easy to chemically react with the metal materials, so that the performance of the perovskite light absorption layer is rapidly reduced, and the stability of the performance of the detector is influenced. Meanwhile, the perovskite material is also easily affected by external conditions such as water, oxygen and the like, and chemical reaction occurs. As the interface layer separates the perovskite light absorption layer from the top electrode and from the signal reading thin film transistor array, the perovskite material can be prevented from reacting with the top electrode and the metal material of the signal reading thin film transistor array, and the perovskite material is protected from being influenced by external conditions such as water, oxygen and the like, so that the long-term stability of the performance of the perovskite detector is ensured.
Drawings
Fig. 1 shows a schematic view of a semiconductor-type X-ray detector, wherein 1 denotes a top electrode; 2 represents a first interface layer; 3 represents a perovskite light-absorbing layer; 4 represents a second interface layer; 5 represents a signal readout thin film transistor array; the parts represented by numerals are only schematically shown and do not represent actual size ratios;
FIG. 2 shows the cubic structure of a perovskite material, wherein A represents a metal cation or an organic cation, B represents a metal cation, and X represents a halide anion;
FIGS. 3 and 4 show the results of sensitivity tests carried out using as a representative detector of the present invention a perovskite semiconductor type X-ray detector (including a first interface layer of polyimide and a second interface layer of a blend material of polyimide and CsPbI3, which is an organic material) produced in example 13 of the present invention, and using as a detector for comparison a perovskite semiconductor type X-ray detector not including the first interface layer and the second interface layer of example 13;
FIGS. 5 and 6 show a perovskite semiconductor type X-ray detector (containing an organic material polyimide and CsPbI) produced in example 14 of the present invention3Blend material first interface layer and alumina second interface layer) as a representative detector of the present invention, and a perovskite semiconductor type X-ray detector not containing the first interface layer and the second interface layer of example 14 as a detector for comparison, the result of response speed test was performed.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and the attached drawings. It is noted that all scientific and technical terms used herein have the same meaning as is familiar to those skilled in the art, unless defined otherwise.
Structure of perovskite semiconductor type X-ray detector
The invention discloses a novel perovskite semiconductor type X-ray detector on one hand. Referring to fig. 1, the perovskite semiconductor type X-ray detector of the present invention has a multilayer planar structure, and includes the following parts from bottom to top: a top electrode (1); a first interface layer (2); a perovskite light-absorbing layer (3); a second interface layer (4); and a signal readout thin film transistor array (5) (comprising a signal output circuit). These components are described in detail below.
1. Top electrode
The top electrode and a signal output circuit integrated in the signal reading thin film transistor array form an electrode group for respectively leading out photo-generated electrons and holes generated by the light absorption layer. During the operation of the detector, X-rays firstly penetrate through the top electrode and enter the light absorption layer, are absorbed by the light absorption layer and are converted into electric signals. Therefore, the ideal top electrode material should have good conductivity and not impair the absorption of X-rays by the light-absorbing layer. Commonly used top electrode materials include metal materials such as molybdenum (Mo), silver (Ag), and gold (Au), carbon materials such as graphene, carbon nanotubes, and carbon fibers, and metal oxide materials such as Indium Tin Oxide (ITO) and tin oxide coating (FTO). These top electrode materials have good electrical conductivity.
2. Perovskite light-absorbing layer
The light absorption layer generates photo-generated electrons and holes by absorbing X-rays, so that a directional photocurrent is generated under the action of an external bias voltage and is the most core part in the whole detector. The photoelectric properties of the light-absorbing layer material play a decisive role in the performance of the detector. The X-ray absorption capacity, the carrier migration length and the carrier life of the light absorption layer material in unit volume influence the number of photon-generated carriers and the magnitude of photoconductive gain, so that the intensity of the photoresponse signal current is fundamentally determined. In addition, the magnitude of the dark state current of the detector assembly is also related to the self-resistance of the light absorbing layer material. Currently, the mainstream light absorbing layer materials of the detector comprise monocrystalline silicon, polycrystalline selenium, cadmium telluride materials and the like. The light absorbing layer materials have high manufacturing cost, are difficult to realize high X-ray absorption and excellent carrier transmission capability simultaneously in performance, have low effective conversion capability on X-rays, and have toxicity.
In recent years, perovskite materials have attracted much attention due to their outstanding photoelectric properties and low production costs, and are considered as revolutionary light-absorbing layer materials. The perovskite material belongs to a cubic crystal system, and the structural formula is generally written as ABX3Wherein A represents a metal cation or an organic cation, B represents a metal cation, and X represents a halogen anion (see FIG. 2). A and X form an octahedral structure [ AX ] through a strong coordination bond6]4-A is located at the center of the octahedron, X is located at the apex of the octahedron, and B fills the voids formed by the octahedral three-dimensional network. Compared with the traditional light absorption layer materials such as polycrystalline selenium and the like, the perovskite material has higher carrier mobility and carrier service life, and the constituent atoms of the perovskite material have larger average atomic number, so that the sensitivity of the semiconductor type X-ray detector based on the perovskite material light absorption layer is greatly superior to that of the commercial polycrystalline selenium semiconductor X-ray detector at present, the X-ray imaging quality can be improved, the X-ray dosage required by imaging can be greatly reduced, and the radiation damage to organisms in the testing process can be reduced.
In 2015, organic-inorganic hybrid perovskite MAPbI3The material is firstly applied to a light absorption layer (Nature photon.2015, 9 and 44) of a semiconductor type X-ray detector, and the sensitivity of the prepared X-ray detector exceeds that of a commercial polycrystalline selenium semiconductor X-ray detector (the sensitivity of the X-ray detector is only 20 mu C Gy at most)air -1cm-2). During the following one or two years, a series of MAPbX with organic-inorganic hybrid perovskite is reported3(X ═ Cl, Br, I) semiconductor-type X-ray detector based on MAPbBr as light-absorbing layer material3The X-ray detector of the single crystal light absorption layer realizes 2.1 × 104μC Gyair -1cm-2High sensitivity (naturepthon.2017, 11, 315), more practical MAPbI3The sensitivity of the polycrystalline film X-ray detector reaches 1.1 × 104μC Gyair -1cm-2(Nature.2017, 550, 87) and high-definition medical X-ray imaging is realized. Inorganic perovskite material CsPbX3(X ═ Cl, Br, I) materials are considered calciumCompared with organic-inorganic hybrid perovskite materials, the most potential light absorption layer material of the X-ray detector in titanium ore materials has higher material density and higher average atomic number, so that the X-ray absorption capacity is stronger4μCGyair -1cm-2(Adv.Mater.2019，31，1904405)。
The perovskite material suitable for the light absorption layer of the perovskite semiconductor type X-ray detector comprises an inorganic perovskite material and organic-inorganic hybrid perovskite. Non-limiting examples of inorganic perovskites include, but are not limited to, CsPbX3And CsSnX3Wherein X is one or more of I, Br and CI. Non-limiting examples of materials for organic-inorganic hybrid perovskite layers include, but are not limited to, CH3NH3PbI3(MAPbI3)、CH3NH3PbCl3、CH3NH3PbBr3、CH3CH2NH3PbCl3、CH3CH2NH3PbBr3、CH3CH2NH3PbI3、NH2CH＝NH2PbCl3、NH2CH＝NH2PbBr3And NH2CH＝NH2PbI3。
Generally, the perovskite material has high carrier mobility, and can be used as a high-efficiency light absorption layer material without additional doping ions. However, the constituent elements in the pure inorganic perovskite material and the pure organic-inorganic hybrid perovskite material can be partially replaced by other elements, i.e. a doped perovskite material is formed, which can further improve the performance of the light absorbing layer as the light absorbing layer material, and can also be used for the light absorbing layer of the perovskite semiconductor type X-ray detector of the invention. Further, a mixed layer formed by stacking a plurality of perovskite material layers or a mixed layer formed by stacking a non-perovskite material and a perovskite material may be used as a light absorbing layer of the perovskite semiconductor type X-ray detector of the present invention.
3. Signal readout thin film transistor array
The signal readout thin film transistor array mainly comprises a pixilated electrode, a preposed signal amplifier, a pixilated capacitor and a pixilated Thin Film Transistor (TFT). The pixilated electrode is used for collecting charges generated in a certain pixel area after the semiconductor material absorbs X-rays, and the material of the electrode is any one or more of gold, silver, copper, aluminum, molybdenum, nickel, indium tin oxide, indium zinc oxide, transparent conductive plastic and conductive compound, or heavily doped semiconductor material. The preposed signal amplifier is used for amplifying the signal and improving the on-off ratio of the original signal. The pixel capacitor is connected with the pixel electrode and used for storing the charges collected by the pixel electrode. The pixelized thin film transistor is generally divided into: a reset transistor, connected to the pixel charge, for clearing the charge in the capacitor; a buffer transistor that converts the current signal into an ionization signal; and a column pass gate transistor which integrates the column pass gate signal and the row pass gate signal for outputting an entire column integrated signal.
The perovskite semiconductor type X-ray detector of the invention can adopt a signal readout thin film transistor array known in the art, and the size of the signal readout thin film transistor array can be 0.1-100cm2In the meantime.
4. Interfacial layer
The perovskite semiconductor type X-ray detector is innovative in that a first interface layer is arranged between the top electrode and the perovskite light absorption layer, and a second interface layer is arranged between the perovskite light absorption layer and the signal reading thin film transistor array. The first interface layer and the second interface layer each independently have a thickness of between 1nm and 10 μm. Within this thickness range, the first interface layer organic material absorbs very little X-rays and does not significantly affect detector performance.
The materials of the first interface layer and the second interface layer are each independently one or a combination of two or more of an organic material, an inorganic material, and a perovskite material, provided that the perovskite materials of the first interface layer and the second interface layer are different perovskite materials from the perovskite materials of the perovskite light absorbing layer. In a specific embodiment, the combination of two of the organic material, the inorganic material, the perovskite material is a blended material, the blending ratio thereof being any blending ratio, such as from 0.1: 99.9 to 99.9: 1, or any ratio therebetween. In general, it is convenient to employ an equal ratio of 1: 1. The above-described setting of the ratio of proportions is also applicable to a combination of three of organic materials, inorganic materials, and perovskite materials.
The organic material used as the interface layer material may be an organic polymer or an organic small molecule compound. Preferably, the organic material used as the interface layer material is polyimide, carbon 60, Polymethylmethacrylate (PMMA), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA) or PCBM ([6, 6] -phenyl-C61-methyl butyrate).
The inorganic material used as the interface layer material may be a metal oxide, a metal sulfide, a metal simple substance, or a carbon material. Preferably, the inorganic material used as the interface layer material includes, but is not limited to, titanium oxide, tin oxide, nickel oxide, aluminum oxide, zirconium sulfide, bismuth metal, graphite, or carbon black.
The perovskite material used as the interface layer material may be an inorganic perovskite material or an organic-inorganic hybrid perovskite material. Specific examples can be found in the description of the perovskite light absorbing layer above.
4.1. A first interface layer
The first interface layer is arranged between the top electrode and the perovskite light absorption layer and has the following functions:
(1) as an electron/hole transport layer. This helps to extract electrons or holes from the perovskite and promotes electron-hole pair separation, thereby enhancing the photocurrent signal and improving the operating efficiency of the detector. Organic materials such as PCBM, Bis-C60, PTAA and the like and materials such as TiO2、SnO2Oxides have this effect in particular.
(2) The on-off ratio is improved. Suitable interfacial layers can produce tunneling effects at thicknesses on the order of nanometers. In addition, the appropriate interface layer can realize unidirectional conduction of electrons or holes (rectification effect) or other special surface effects through energy band adjustment, so that the switching ratio (photocurrent/dark current) of the detector is effectively improved. High molecular polymer such as polyimide and the like, and Al2O3、CuO2Oxides have this effect in particular.
(3) The current drift is reduced, and the response speed is improved. Perovskite materials can cause serious ion migration phenomenon under the condition of an external electric field due to self-lattice defects and the like. The appropriate interface layer can well passivate the defects on the surface of the perovskite, and effectively inhibit the ion migration of the perovskite material, thereby reducing the current drift. Organic substances such as polymer polymers such as polyimide and PCBM, and Al2O3Oxides have this effect in particular.
(4) Reduce noise, adjust dark current level. Some interface layer materials have higher resistance, and the overall resistance of the detector can be adjusted, so that the dark current is adjusted, and the noise level is also reduced under the condition that the dark current is reduced. For example high-resistance organic polymers and for example Al2O3Etc. oxide or other semiconductor materials have this effect in particular.
(5) And (4) connecting. Good contact between the perovskite layer and the top electrode is required to produce an effective detection signal. Organic materials, especially high molecular organic polymers, have the characteristics of unique expansion coefficient, surface tension, elastic plasticity and the like, while inorganic materials, especially inorganic materials with special structures (such as whole columns or mesoporous structures), increase the contact area with the perovskite layer under a proper preparation method, and can improve the adhesion of the perovskite layer and the top electrode to form close and effective contact. This effect is particularly exhibited by high molecular polymers such as polyimide and oxides such as mesoporous TiO 2.
(6) As a protective layer. The perovskite material itself is susceptible to reactions or phase changes under the action of water, oxygen or other polar molecules, resulting in degradation of the detector performance. The dense interfacial layer can effectively block water, oxygen, or other polar molecules from entering the perovskite layer. Polymers such as PMMA and, for example, most oxides, elemental carbon or a small portion of elemental metals such as bismuth metal, among others, have this effect.
In the present invention, the organic material and/or the inorganic material in a single first interface layer may play one or more of the above-described roles.
In addition, the mixed first interface layer containing a perovskite material and an organic material and/or an inorganic material has the function of the perovskite material in addition to the above-described function of the organic material and/or the inorganic material. Specifically, the perovskite material in the first interface layer has low partial resistivity and good compatibility with a perovskite layer, and perovskite crystals wrapped by a polymer can be formed in the process of forming the interface layer. By adjusting the ratio of perovskite to organic material, the resistivity of the first interfacial layer can be controlled. Compared with a pure organic material interface layer, the perovskite-doped interface layer has the function of increasing adhesion and simultaneously has lower resistance under the same thickness, and particularly under certain conditions, a tunneling effect can occur when a polymer layer is thinner, so that the performance of the detector is improved.
4.2. Second interface layer
The second interface layer is arranged between the perovskite light absorption layer and the signal readout thin film transistor array. Since the order in which the second interfacial layer receives X-rays is behind the perovskite, the absorption of X-rays by the perovskite is generally not affected. The second interface layer has the following effects.
(1) As an electron/hole transport layer. This helps to extract electrons or holes from the perovskite and promotes electron-hole pair separation, thereby enhancing the photocurrent signal and improving the operating efficiency of the detector. Organic materials such as PCBM, Bis-C60, PTAA, PPDI 6 and the like and organic materials such as TiO2、SnO2Oxides have this effect in particular.
(2) The on-off ratio is improved. Suitable interfacial layers can produce tunneling effects at thicknesses on the order of nanometers. In addition, the appropriate interface layer can realize unidirectional conduction of electrons or holes (rectification effect) or other special surface effects through energy band adjustment, so that the switching ratio (photocurrent/dark current) of the detector is effectively improved. High molecular polymer such as polyimide and the like, and Al2O3、CuO2Oxides have this effect in particular.
(3) The current drift is reduced, and the response speed is improved. The perovskite material is due to self-lattice defects, etc. inUnder the condition of an external electric field, serious ion migration phenomenon can be generated. The appropriate interface layer can well passivate the defects on the surface of the perovskite, and effectively inhibit the ion migration of the perovskite material, thereby reducing the current drift. Polymers such as polyimide, organic materials such as PCBM, and alloys such as Al2O3Oxides have this effect in particular.
(4) Reduce noise, adjust dark current level. Some interface layer materials have higher resistance, and the overall resistance of the detector can be adjusted, so that the dark current is adjusted, and the noise level is also reduced under the condition that the dark current is reduced. For example high-resistance organic polymers and for example Al2O3Etc. oxide or other semiconductor materials have this effect in particular.
(5) And (4) connecting. Good contact between the perovskite layer and the underlying circuitry is required to produce an effective detection signal. Organic materials, especially high molecular organic polymers, have the characteristics of unique expansion coefficient, surface tension, elastic plasticity and the like, while inorganic materials especially have inorganic matters with special structures (such as whole columns or mesoporous structures), and can increase the contact area with a perovskite layer under a proper preparation method, so that the adhesion of the perovskite layer and a bottom circuit can be improved, and the tight and effective contact is formed. High molecular polymer such as polyimide and mesoporous TiO2Oxides have this effect in particular.
(6) As a protective layer. The perovskite material itself is susceptible to reactions or phase changes under the action of water, oxygen or other polar molecules, resulting in degradation of the detector performance. The dense interfacial layer can effectively block water, oxygen, or other polar molecules from entering the perovskite layer. Polymers such as PMMA and, for example, most oxides, carbon or a small proportion of metal elements have this effect in particular.
In the present invention, the organic material and/or the inorganic material in the single second interface layer may play one or more of the above-described roles.
In addition, for the mixed second interface layer comprising a perovskite material and an organic material and/or an inorganic material, which has the effect of the perovskite material in addition to the above-described effect of the organic material and/or the inorganic material, see in particular the above description for the first interface layer.
Preparation of perovskite semiconductor type X-ray detector
On the other hand, the invention discloses a preparation method of the perovskite semiconductor type X-ray detector. Briefly, referring to fig. 1, the method of manufacturing the present invention uses a signal readout thin film transistor array of an existing semiconductor type X-ray detector, first prepares a second interface layer thereon, then prepares a perovskite light absorption layer on the second interface layer, then prepares a first interface layer on the perovskite light absorption layer, then prepares a top electrode on the first interface layer, and finally manufactures the perovskite semiconductor type X-ray detector of the present invention.
1. Fabricating a second interface layer on the signal readout thin film transistor array
The invention does not relate to the innovation of a signal reading thin film transistor array, and the preparation method of the invention can adopt the signal reading thin film transistor array of the existing semiconductor type X-ray detector. The second interface layer may be formed on the signal readout thin film transistor array by evaporation, spin coating, spray coating, or doctor blading, which are commonly used in the art.
The evaporation method generally involves placing a pure interface layer material in a tungsten boat of an evaporator, placing the signal readout thin film transistor array substrate in an evaporation chamber, evaporating the interface layer material under conditions of high vacuum degree and the like, and gradually depositing the interface layer material on the signal readout thin film transistor array to form a second interface layer. The evaporation voltage is 1-1.5V, the current is 80-120mA, and the vacuum degree is 10-4Pa or less.
Spin coating typically involves formulating a solution of the interface layer precursor with a suitable solvent, preferably an organic solvent such as chlorobenzene, DMSO, DMF or gamma-butyrolactone, which may be present in a concentration of 0.1 to 5 mol/ml. Fixing the signal readout thin film transistor array on a turntable, dripping the solution on the signal readout thin film transistor array, throwing out the redundant solution by utilizing the rotation of the turntable and forming a uniform wet film on the signal readout thin film transistor arrayAnd then heating to remove the solvent of the wet film, and finally forming a compact second interface layer. For example, an interface layer precursor solution can be prepared by weighing a certain amount of interface layer precursor, such as 1-10g of tetrabutyl titanate (precursor of inorganic interface layer titanium oxide), adding into a beaker, adding a certain amount of suitable solvent (such as 10-100ml of chlorobenzene), stirring and mixing uniformly. And fixing the signal reading thin film transistor array on a turntable, and then dripping the interface layer precursor solution on the signal reading thin film transistor array. Usually in the range of per cm2Preparing an interface layer 100 μm thick over the interface layer area requires dropping 10-100ml of precursor solution.
The amount can be 100-500. mu.L of precursor solution. The rotating disc rotates at the rotating speed of 2000 plus 8000rps to throw off the redundant solution to form a uniform wet film. Then standing for 1-3min, and heating at 100-120 ℃ to remove the solvent of the wet film, thereby finally forming a compact second interface layer.
The doctor blade process typically involves preparing a solution of the interface layer precursor with a suitable solvent and then using a doctor blade to doctor blade the solution onto the signal sensing thin film transistor array to form a uniform wet film. Typically, the squeegee is 10-100 μm from the surface of the signal sensing TFT array and the speed of the squeegee is 1-20 cm/s. And heating at 50-100 ℃ to remove the solvent of the wet film, and finally forming a compact second interface layer. The preparation of the solution of the interface layer precursor may be referred to, for example, spin coating.
The spray coating process typically involves formulating a solution of the interface layer precursor with a suitable solvent, typically at a precursor concentration of 0.1-3 mol/ml. Then, an ultrasonic spraying device (comprising an ultrasonic generator, a carrier gas device and a nozzle device) is adopted to spray the solution into aerosol or small liquid drops, a uniform wet film is formed on the signal reading thin film transistor array, the solvent of the wet film is removed by heating, and finally a compact second interface layer is formed. For example, an interface layer precursor solution can be prepared by weighing a certain amount of interface layer precursor (e.g., 1-10g of tetrabutyl titanate), adding into a beaker, adding a certain amount of suitable solvent (e.g., 100-1000ml of chlorobenzene), and stirring and mixing uniformly. Injecting 10-100ml of precursor solution of the interface layer into an ultrasonic generator, adjusting power to generate a large number of precursor droplets, then utilizing a carrier gas device and a spray head device, wherein the distance of the spray head is 1-20cm, spraying the precursor solution droplets onto a signal reading thin film transistor array substrate under the pressure of 1-10Pa, and removing the solvent to form a film under the heating of 100-150 ℃.
It should be noted that, since the second interface layer is prepared on the signal readout thin film transistor array, the conditions for preparing the second interface layer cannot cause the signal readout thin film transistor array to be damaged, and especially, the heating temperature of the spin coating method and the doctor blade method is not too high, and is generally controlled below 300 ℃, and is generally controlled between 50 ℃ and 200 ℃.
2. Preparing a perovskite light-absorbing layer on the second interface layer
After a second interface layer is prepared on the signal readout thin film transistor array, a second interface layer/transistor array semi-finished product is obtained, and then a perovskite light absorption layer is prepared on the second interface layer. The preparation method of the perovskite light absorption layer comprises a spin coating method, a blade coating method, a spraying method and a single crystal growth method. Typically, the thickness of the perovskite light absorbing layer is controlled to be from 100nm to 10 cm.
Spin coating typically involves preparing a solution of the perovskite precursor with a suitable solvent, fixing the second interface layer/semi-finished transistor array on a rotating disk, then dropping the solution onto the second interface layer, spinning off excess solution with the rotation of the rotating disk and forming a uniform wet film on the second interface layer, and then heating to remove the solvent from the wet film and finally form a dense perovskite light-absorbing layer.
The blade coating method comprises the steps of preparing a solution of a perovskite precursor by using a proper solvent, then blade coating the solution on a second interface layer/a second interface layer of a semi-finished product of the transistor array by using a scraper to form a uniform wet film, and heating to remove the solvent of the wet film so as to finally form a compact perovskite light absorption layer.
The spraying method is an aerosol-based cold deposition method, and relates to a method for preparing a perovskite precursor solution by using a proper solvent, then spraying the solution into aerosol or small droplets by using ultrasonic spraying equipment (comprising an ultrasonic generator, carrier gas equipment and a nozzle equipment), forming a uniform wet film on a second interface layer of a second interface layer/transistor array semi-finished product, and heating to remove the solvent of the wet film to finally form a compact perovskite light absorption layer.
The parameters of the spin coating method, the blade coating method and the spray coating method can be referred to the respective methods in the preparation of the second interface layer described above.
The single crystal growth method involves preparing a solution of a perovskite precursor in a suitable solvent, then growing single crystal nuclei from the solution at an elevated temperature, removing the nuclei, transferring the resulting nuclei into a new clear perovskite solution, and then heating and holding the temperature to continue the growth. For example, growth can be continued by heating in an oil bath at 100-. It is also possible to heat the crystal until the crystal grows to a side length of more than 10cm, for example.
3. Preparing a first interface layer on the perovskite light absorption layer
And preparing a perovskite light absorption layer on the second interface layer to obtain a perovskite light absorption layer/second interface layer/transistor array semi-finished product, and then preparing a first interface layer on the perovskite light absorption layer. Similar to the preparation of the second interface layer on the signal readout thin film transistor array, evaporation, spin coating, spray coating, and doctor blading may be employed, which is not described in detail herein.
It should be noted that, since the first interface layer is prepared on the perovskite light-absorbing layer, the conditions for preparing the first interface layer cannot cause the perovskite light-absorbing layer to be damaged, and particularly, the heating temperature of the spin coating method and the doctor blade method is not too high and is generally controlled to be between 100 ℃ and 120 ℃.
4. Preparing a top electrode on the first interface layer
After a first interface layer is prepared on the perovskite light absorption layer, a first interface layer/the perovskite light absorption layer/a second interface layer/a transistor array semi-finished product is obtained, and then a top electrode is prepared on the first interface layer. Top electrode materials of semiconductor X-ray detectors commonly used in the art include metal materials such as molybdenum (Mo) and silver (Ag), carbon materials such as graphene, carbon nanotubes and carbon fibers, and metal oxide materials such as Indium Tin Oxide (ITO). The top electrode can be prepared by a blade coating method, a spraying method, an evaporation method or a magnetron sputtering method.
The blade coating method is mainly suitable for preparing carbon electrodes with the thickness of 1-50 mu m. Generally, a small amount of an organic solvent is added to a carbon material to prepare a viscous carbon slurry, and the slurry is uniformly stirred. Covering a template on the first interface layer/perovskite light absorption layer/second interface layer/first interface layer of the transistor array semi-finished product, and then smearing carbon slurry on the template. And adjusting parameters of the blade coating instrument, including the distance between the scraper and the surface of the detector, the moving speed of the scraper and the number of times of back and forth, so that the scraper horizontally scrapes the carbon slurry at a certain speed, and after the carbon slurry is uniformly coated, the template is removed. And transferring the first interface layer/perovskite light absorption layer/second interface layer/transistor array semi-finished product coated with the carbon electrode wet film to a heating table, heating at 100 ℃ for 30min, and removing the organic solvent to obtain a uniform carbon electrode on the first interface layer.
The spraying method can prepare nano metal electrodes (including Au and Ag). The spraying method can be divided into a cold spraying method and a hot spraying method, wherein the cold spraying method directly utilizes high-pressure carrier gas to spray metal simple substance powder or metal nanowires to a target deposition surface, and the hot spraying method firstly generates high-temperature flame flow through supersonic flame and other means, utilizes the action of the flame flow and the metal simple substance powder, and then accelerates the deposition through jet flow to the target deposition surface. By changing parameters such as spraying temperature, spraying time and the like, metal electrodes with the thickness of 5nm to 5 mu m and electrodes with special shapes such as nano wires and the like can be prepared. Therefore, the metal electrode can be prepared on the first interface layer of the semi-finished product of the first interface layer/the perovskite light absorption layer/the second interface layer/the transistor array by adopting the spraying method.
The evaporation method generally involves placing the top electrode material in a tungsten boat of an evaporator, evaporating the top electrode material under conditions of high vacuum, etc., and gradually depositing it onto the first interface layer of the first interface layer/perovskite light absorbing layer/second interface layer/transistor array semifinished product.
The magnetron sputtering method generally involves placing the top electrode material in a magnetron sputtering apparatus as a target and sputtering at high speed at low gas pressure onto the first interface layer/perovskite light absorbing layer/second interface layer/first interface layer of the semi-finished transistor array.
It should be noted that in the preparation of the first interface layer and the second interface layer, the interface layer precursor may be a single organic material or a single inorganic material, or a mixture of an organic material and an inorganic material, or a mixture of a perovskite and an organic material, or a mixture of a perovskite and an inorganic material, or a mixture of a perovskite and an organic material and an inorganic material, or a mixture of different perovskite materials. The molar ratio of perovskite material to organic or inorganic material, or the molar ratio of two different perovskite materials, may be from 1: 2 to 2: 1.
It should furthermore be mentioned that the first or second interface layer or the perovskite layer can also each be produced from a stack of layers, the materials of each layer being identical or different or being mixtures of two or more materials. Preferably, the materials of adjacent layers are different or not identical to achieve a superposition of the functions of two or more different materials or to improve the function of one of the materials.
The invention will be further illustrated by means of specific embodiments in conjunction with the accompanying drawings. It should be understood that the examples are illustrative only and are not to be construed as limiting the scope of the invention. The experimental procedures in the following examples are carried out in the usual manner unless otherwise specified. Materials, reagents, instruments and the like used in the following examples are commercially available unless otherwise specified. Any methods and materials similar or equivalent to those described below can be used in the present invention.
Example 1
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of Indium Tin Oxide (ITO) material, and the perovskite light absorption layer is made of inorganic perovskite material CsPbI3The first interface layer is made of inorganic material titanium oxide, and the second interface layer is also made of inorganic material titanium oxide. Selecting commercially available 1cm2The perovskite semiconductor type X-ray detector is prepared on the basis of the signal reading thin film transistor array.
Firstly, 10g of tetrabutyl titanate (precursor of titanium oxide) is weighed and placed in a beaker, then 100ml of chlorobenzene solvent is added, and the mixture is stirred and mixed uniformly to prepare a titanium oxide precursor solution. 50mL of precursor solution is dripped on a signal reading thin film transistor array, the signal reading thin film transistor array is fixed on a turntable of a table homogenizer (KW-4A, institute of microelectronics of Chinese academy of sciences), the turntable rotates at the rotating speed of 5000rps, surplus solution is thrown out, a uniform wet film is formed on a circuit of the signal reading thin film transistor array, and then the solution is heated on a hot table at 100 ℃ to remove the solvent of the wet film, and finally a compact second interface layer is formed, so that a second interface layer/transistor array semi-finished product is obtained.
Then, 10g of the inorganic perovskite material CsPbI was weighed3And putting the mixture into a beaker, adding 100ml of DMSO, and stirring and mixing uniformly to prepare the perovskite precursor solution. Dropping 100mL of precursor solution on a second interface layer of the second interface layer/transistor array semi-finished product, fixing the semi-finished product on a turntable, rotating the turntable at the rotating speed of 5000rps, throwing out redundant solution, forming a uniform wet film on the second interface layer, heating on a hot table at 100 ℃ to remove the solvent of the wet film, and finally forming a compact perovskite light absorption layer to obtain the perovskite light absorption layer/second interface layer/transistor array semi-finished product.
Then, preparing a titanium oxide precursor solution in the same manner, and preparing a first interface layer in the same spin coating manner to obtain a semi-finished product of a second interface layer/transistor array/perovskite light absorption layer/first interface layer.
Finally, the semi-finished product obtained is placed in a vacuum thermal evaporator (Shenyang Corcheng vacuum Co.) at 104And evaporating Indium Tin Oxide (ITO) onto the semi-finished product under high vacuum with the pressure of Pa below to finally prepare the perovskite semiconductor type X-ray detector.
Example 2
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of Indium Tin Oxide (ITO) material, and perovskite absorbs lightThe layer adopts an inorganic perovskite material CsPbI3The first interface layer adopts titanium oxide as an inorganic material, and the second interface layer adopts polyimide as an organic material. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. The second interface layer was prepared by preparing a polyimide precursor solution and preparing it in a similar manner to example 1. The polyimide precursor solution is prepared by weighing 10g of polyamic acid (precursor of polyimide), placing in a beaker, adding 100ml of DMSO solvent, stirring and mixing uniformly. The remaining layers (including the top electrode) can be prepared in the manner referred to in example 1.
Example 3
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of Indium Tin Oxide (ITO) material, and the perovskite light absorption layer is made of inorganic perovskite material CsPbI3The first interface layer is made of organic polyimide, and the second interface layer is also made of organic polyimide. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. Each layer (including the top electrode) can be prepared in the manner referred to in example 2.
Example 4
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of Indium Tin Oxide (ITO) material, and the perovskite light absorption layer is made of inorganic-organic hybrid perovskite material CH3NH3PbI3(MAPbI3) The first interface layer is made of inorganic material titanium oxide, and the second interface layer is also made of inorganic material titanium oxide. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. For perovskite light-absorbing layers, as in example 1Preparation of inorganic-organic hybrid perovskite Material CH3NH3PbI3(MAPbI3) Precursor solution and preparing perovskite light absorption layer. The remaining layers (including the top electrode) can be prepared in the manner referred to in example 1.
Example 5
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of Indium Tin Oxide (ITO) material, and the perovskite light absorption layer is made of inorganic-organic hybrid perovskite material CH3NH3PbI3(MAPbI3) The first interface layer is made of inorganic material alumina, and the second interface layer is made of organic material polyimide. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. Each layer (including the top electrode) can be prepared in the manner described for the preparation of the layer of the corresponding material in examples 1-4.
Example 6
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of tin oxide (FTO) material, and the perovskite light absorption layer is made of inorganic-organic hybrid perovskite material CH3NH3PbI3(MAPbI3) The first interface layer is made of organic polyimide, and the second interface layer is also made of organic polyimide. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. Each layer (including the top electrode) can be prepared in the manner described for the preparation of the layer of the corresponding material in examples 1-4.
Example 7
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; calcium carbonateA titanium ore light absorption layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of tin oxide (FTO) material, and the perovskite light absorption layer is made of inorganic perovskite material CsPbI3The first interface layer is made of organic polyimide, and the second interface layer is made of inorganic-organic hybrid perovskite material CH3NH3PbI3(MAPbI3). The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. Each layer (including the top electrode) can be prepared in the manner described for the preparation of the layer of the corresponding material in examples 1-4.
Example 8
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of tin oxide (FTO) material, and the perovskite light absorption layer is made of inorganic-organic hybrid perovskite material CH3NH3PbI3(MAPbI3) The first interface layer is made of organic polyimide, and the second interface layer is made of inorganic perovskite CsPbI3. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. Each layer (including the top electrode) can be prepared in the manner described for the preparation of the layer of the corresponding material in examples 1-4.
Example 9
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of tin oxide (FTO) material, and the perovskite light absorption layer is made of inorganic perovskite material CsPbI3The first interface layer adopts inorganic-organic hybrid perovskite material CH3NH3PbI3(MAPbI3) And the second interface layer is made of organic polyimide. The same signal readout sheet as in example 1 was selectedA perovskite semiconductor type X-ray detector is prepared on the basis of the film transistor array. Each layer (including the top electrode) can be prepared in the manner described for the preparation of the layer of the corresponding material in examples 1-4.
Example 10
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of tin oxide (FTO) material, and the perovskite light absorption layer is made of inorganic-organic hybrid perovskite material CH3NH3PbI3(MAPbI3) The first interface layer adopts an inorganic perovskite material CsPbI3And the second interface layer is made of organic polyimide. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. Each layer (including the top electrode) can be prepared in the manner described for the preparation of the layer of the corresponding material in examples 1-4.
Example 11
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of Indium Tin Oxide (ITO) material, and the perovskite light absorption layer is made of inorganic-organic hybrid perovskite material CH3NH3PbI3(MAPbI3) The first interface layer adopts an inorganic perovskite material CsPbI3The second interface layer is made of organic material polyimide and CH3NH3PbI3(MAPbI3) 1: 1 of the blend material. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. Each layer (including the top electrode) can be prepared in the manner described for the preparation of the layer of the corresponding material in examples 1-4.
Example 12
The structure of the perovskite semiconductor type X-ray detector of the present embodiment is shown in FIG1, from bottom to top, comprising the following parts: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of Indium Tin Oxide (ITO) material, and the perovskite light absorption layer is made of inorganic-organic hybrid perovskite material CH3NH3PbI3(MAPbI3)3The first interface layer is made of organic material polyimide and CH3NH3PbI3(MAPbI3) The second interface layer is made of organic polyimide and CsPbI31: 1 of the blend material. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. Each layer (including the top electrode) can be prepared in the manner described for the preparation of the layer of the corresponding material in examples 1-4.
Example 13
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of tin oxide (FTO) material, and the perovskite light absorption layer is made of pure inorganic perovskite material CsPbI3The first interface layer adopts organic polymer polyimide of inorganic perovskite material, and the second interface layer adopts organic polymer polyimide and CsPbI31: 1 of the blend material. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. Each layer (including the top electrode) can be prepared in the manner described for the preparation of the layer of the corresponding material in examples 1-4.
Example 14
The perovskite semiconductor type X-ray detector of the present embodiment is configured, referring to fig. 1, including the following parts from bottom to top: a top electrode 1; a first interface layer 2; a perovskite light-absorbing layer 3; a second interface layer 4; the signal reading thin film transistor array 5. In this embodiment, the top electrode is made of tin oxide (FTO) material, and the perovskite light absorption layer is made of pure inorganic perovskite material CsPbI3The first interface layer adoptsOrganic material polyimide and CsPbI3The second interface layer is made of alumina. The same signal readout thin film transistor array as in example 1 was selected, and a perovskite semiconductor type X-ray detector was prepared on the basis thereof. Each layer (including the top electrode) can be prepared in the manner described for the preparation of the layer of the corresponding material in examples 1-4.
Effect of the perovskite semiconductor type X-ray Detector of the present invention
The perovskite semiconductor type X-ray detector has low signal-to-noise ratio and good response speed, adhesion and stability.
(1) Signal to noise ratio
The signal-to-noise ratio refers to the ratio of a signal to noise in an electronic device or electronic system, wherein the signal refers to an electronic signal from outside the device that needs to be processed by the device, and the noise refers to an irregular additional signal (or information) that does not exist in an original signal after passing through the device, and the additional signal does not change with the change of the original signal. In particular, in an X-ray detector, the total noise includes a sum of various noises such as thermal noise, optical noise, shot noise, etc., which are mainly related to the properties of the semiconductor material selected for the detector and the detection conditions. After the interface layer is added, the noise level remains substantially unchanged under the same probing conditions. The signals are different, and after the interface layer is added, the intensity of the signals can be greatly improved by generating an electron injection effect induced by illumination or generating a tunneling effect at the interface. The sensitivity is an important index for measuring the signal intensity of the detector under the unit illumination intensity and the detection area. The sensitivity is defined as: (signal intensity)/(detection area × X-ray intensity).
Perovskite semiconductor type X-ray Detector (containing polyimide first interface layer and organic Material polyimide and CsPbI) manufactured in example 133Blend material second interface layer) as a representative detector of the present invention, a sensitivity test (X-ray light source: brand VJ Technologies, model IXS080BP210P396, digital source table Keithley brand, model 2400), the results are shown in fig. 3 and 4, respectively, comparison of the two figures shows that the detector of the present invention adds first and second interface layers, sensitivity from 1.9 × 10 for the comparative detector5uCmGy-1cm-1Increased to 1.0 × 106uCmGy-1cm-1And the improvement is over five times. Since adding an interface layer does not change the noise level from a mechanism point of view, an increase in sensitivity can correspondingly increase the signal-to-noise ratio.
(2) Speed of response
The perovskite layer surface often has a large number of surface defects that trap a portion of the photo-generated carriers, causing a delay in the signal. And in the case of the interface layer, the defects on the surface of the perovskite can be passivated, the probability of capturing photoelectrons is reduced, and the response speed is further improved. In addition, under the condition of an external electric field, photoinduced carriers can directionally flow between interface layers with proper thickness through a tunnel effect, so that a quick response signal is generated.
Perovskite semiconductor type X-ray Detector (containing organic materials polyimide and CsPbI) manufactured in example 143Blend material first interface layer and alumina second interface layer) as a representative detector of the present invention, a perovskite semiconductor type X-ray detector not containing the first interface layer and the second interface layer of example 14 was used as a comparative detector, and a response speed test (X-ray light source: brand VJ Technologies, model IXS080BP210P 396; digital source table: the brand Keithley; model 2400), the results are shown in fig. 5 and fig. 6, respectively. As can be seen from a comparison of the two figures, the detector of the present invention adds first and second boundary layers, and the response speed (the time taken for the current to rise from the dark state current to 80% of the peak value of the signal current) rises from about 10s for the comparative detector to only 1s, by a factor of about 10.
(3) Adhesion force
In some methods for manufacturing a semiconductor layer of a detector, high-temperature heating for film formation and annealing at a low temperature are required. During annealing, the semiconductor film is likely to be peeled off because the expansion coefficient of the detector circuit board portion is different from that of the perovskite semiconductor material. The perovskite semiconductor type X-ray detector adopts a flexible organic interface layer material or an inorganic interface layer material. The flexible organic interface layer material, especially the high molecular organic polymer, has the characteristics of unique expansion coefficient, surface tension, elastic plasticity and the like; some inorganic interface layer materials, especially inorganic materials with special structures (such as an aligned or mesoporous structure), can increase the contact area with the perovskite layer under a proper preparation method, and can improve the adhesion of the perovskite layer and the substrate to form close and effective contact.
(4) Stability of
The first interface layer and the second interface layer in the perovskite semiconductor type X-ray detector of the present invention may be protective layers. The perovskite material itself is susceptible to reactions or phase changes under the action of water, oxygen or other polar molecules, resulting in degradation of the detector performance. The dense interfacial layer can effectively block water, oxygen, or other polar molecules from entering the perovskite layer.
The present invention has been described above using specific examples, which are only for the purpose of facilitating understanding of the present invention, and are not intended to limit the present invention. Numerous simple deductions, modifications or substitutions may be made by those skilled in the art in light of the teachings of the present invention. Such deductions, modifications or alternatives also fall within the scope of the claims of the present invention.
Claims (10)
1. The perovskite semiconductor type X-ray detector comprises a top electrode, a perovskite light absorption layer and a signal readout thin film transistor array, and is characterized by further comprising a first interface layer and a second interface layer, wherein the first interface layer is located between the top electrode and the perovskite light absorption layer, and the second interface layer is located between the perovskite light absorption layer and the signal readout thin film transistor array.
2. The perovskite semiconductor-type X-ray detector according to claim 1, wherein the materials of the first interface layer and the second interface layer are independently one or a combination of two or more of an organic material, an inorganic material, and a perovskite material, provided that the perovskite material of the first interface layer and the second interface layer is a different perovskite material from the perovskite material of the perovskite light absorbing layer.
3. The perovskite semiconductor type X-ray detector according to claim 2, wherein the organic material is polyimide, carbon 60, polymethyl methacrylate, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], or [6, 6] -phenyl-C61-methyl butyrate.
4. The perovskite semiconductor type X-ray detector as claimed in claim 2, wherein the inorganic material is a metal oxide, a metal sulfide, a metal simple substance, or a carbon material; preferably, the inorganic material is titanium oxide, tin oxide, nickel oxide, aluminum oxide, zirconium sulfide, bismuth metal, graphite, or carbon black.
5. The perovskite semiconductor type X-ray detector as claimed in claim 2, wherein the perovskite material is an inorganic perovskite material or an organic-inorganic hybrid perovskite material.
6. The perovskite semiconductor type X-ray detector as claimed in claim 5, wherein the inorganic perovskite material is CsPbX3Or CsSnX3Wherein X is one or more of I, Br and CI.
7. The perovskite semiconductor type X-ray detector as claimed in claim 5, wherein the organic-inorganic hybrid perovskite material is CH3NH3PbI3、CH3NH3PbCl3、CH3NH3PbBr3、CH3CH2NH3PbCl3、CH3CH2NH3PbBr3、CH3CH2NH3PbI3、NH2CH＝NH2PbCl3、NH2CH＝NH2PbBr3Or NH2CH＝NH2PbI3。
8. The perovskite semiconductor type X-ray detector according to any one of claims 1 to 7, wherein the thickness of the top electrode is 10 to 60 μm, the thickness of the first interface layer is 1 to 10 μm, the thickness of the second interface layer is 1 to 10 μm, and the thickness of the perovskite layer is 10 μm to 10 em.
9. A method of manufacturing the perovskite semiconductor type X-ray detector according to any one of claims 1 to 8, characterized by comprising the steps of: preparing the second interface layer on the signal reading thin film transistor array, preparing the perovskite light absorption layer on the second interface layer, preparing the first interface layer on the perovskite light absorption layer, preparing the top electrode on the first interface layer, and finally preparing the perovskite semiconductor type X-ray detector.
10. The fabrication method according to claim 9, wherein the fabricating the second interface layer on the signal readout thin film transistor array and the fabricating the first interface layer on the perovskite light absorption layer are performed by evaporation, spin coating, spray coating, or blade coating; the perovskite light absorption layer is prepared on the second interface layer by adopting a spin coating method, a blade coating method, a spraying method or a single crystal growth method; and preparing the top electrode on the first interface layer by adopting a blade coating method, a spraying method, an evaporation method or a magnetron sputtering method.
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