CN109585477B - Flat panel detector structure and preparation method thereof - Google Patents
Flat panel detector structure and preparation method thereof Download PDFInfo
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- CN109585477B CN109585477B CN201811283739.2A CN201811283739A CN109585477B CN 109585477 B CN109585477 B CN 109585477B CN 201811283739 A CN201811283739 A CN 201811283739A CN 109585477 B CN109585477 B CN 109585477B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14643—Photodiode arrays; MOS imagers
- H01L27/14658—X-ray, gamma-ray or corpuscular radiation imagers
- H01L27/14663—Indirect radiation imagers, e.g. using luminescent members
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
- G01N23/06—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption
- G01N23/083—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption the radiation being X-rays
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
Abstract
The invention provides a flat panel detector structure and a preparation method thereof, wherein the preparation method comprises the following steps: providing a substrate, and preparing a lower electrode layer on the substrate; providing a radiation absorbing material liquid including a lead-containing compound liquid; coating the radiation absorbing material liquid on the lower electrode layer to prepare a light conversion layer on the lower electrode layer based on the coated radiation absorbing material liquid; and preparing an upper electrode layer on the light conversion layer. The invention improves the material of the existing light conversion layer, improves the ray absorption capacity of the light conversion layer, reduces the thickness of the light conversion layer, designs the forming methods of the light conversion layer and the like, solves the problems existing in the formation of a polycrystalline structure, improves the chemical composition and phase uniformity of a device, improves the uniformity of an image, improves the effective utilization rate of raw materials, simplifies process equipment, designs the structure of a detector, improves the problem of leakage current, reduces the noise of the detector, improves the sensitivity and the contrast, improves the electrode material of the detector, and reduces the cost.
Description
Technical Field
The invention belongs to the technical field of ray detection, and particularly relates to a flat panel detector structure and a preparation method thereof.
Background
X-ray radiation imaging utilizes the characteristics of short wavelength and easy penetration of X-rays and different absorption characteristics of different substances to the X-rays, and imaging is carried out by detecting the intensity of the X-rays penetrating through an object. A direct flat panel detector is a technology for directly converting X-ray photons into carriers (electrons or holes) using a semiconductor material and reading out the carriers for imaging. The direct flat panel detector has the characteristics of high sensitivity and high contrast, and can be applied to the fields of medical radiation imaging, industrial flaw detection, security inspection and the like.
At present, a direct flat panel detector occupies an absolute mainstream based on an amorphous selenium (Se) material, and a light conversion layer (a light conversion layer is also called as a conversion layer and is a film layer for converting high-energy incident X-ray photons into carriers (electron hole pairs)) of a commercial direct X-ray detector consists of the amorphous selenium (Se), and the amorphous selenium material has the advantage of easy large-scale uniform film formation, so that the direct flat panel detector is widely used. However, amorphous selenium materials have the following disadvantages: the crystallization temperature of the amorphous selenium is about 70 ℃, the amorphous selenium becomes polycrystal after crystallization, so that the performance of the device is changed, and the failure of the device is caused under extreme conditions (for example, when the device is transported in a closed air-conditioned compartment in summer, the amorphous selenium film is gradually crystallized into polycrystal due to the long-time high temperature in the compartment, and finally the performance of the product is changed or even fails); since selenium has a low atomic number (34), it has poor absorption of X-rays (particularly high-energy X-rays), and in order to sufficiently absorb X-rays, the thickness of the amorphous selenium film needs to be increased, which leads to: the uniformity of the film layer becomes poor, resulting in deterioration of imaging quality; in order to collect the charges sufficiently, the voltage across the film is increased (e.g., about 2000V when the film thickness is 200um, and about 20000V when the film thickness reaches 2000 um), and the use of the high voltage not only increases the design difficulty and cost of the device, reduces the reliability, but also easily causes potential safety hazards (e.g., leakage) to the operator and the patient.
Therefore, how to provide a flat panel detector structure and a method for manufacturing the same, which are necessary to solve the above-mentioned problems of the prior art and improve the same.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to a flat panel detector structure and a method for manufacturing the same, which are used to solve the problems of poor absorption of the material of the light-transmitting layer in the prior art.
To achieve the above and other related objects, the present invention provides a method for manufacturing a flat panel detector structure, comprising the steps of:
providing a substrate, and preparing a lower electrode layer on the substrate;
providing a radiation absorbing material liquid, wherein the radiation absorbing material liquid includes a lead-containing compound liquid;
coating the radiation absorbing material liquid on the lower electrode layer to prepare a light conversion layer on the lower electrode layer based on the coated radiation absorbing material liquid; and
and preparing an upper electrode layer on the light conversion layer.
As an alternative of the present invention, the lead-containing compound liquid is constituted by a radiation absorbing material including a lead-containing compound and an organic solvent, and the radiation absorbing material is dissolved in the organic solvent to form the lead-containing compound liquid.
As an alternative of the invention, the lead-containing compound comprises PbO, PbO2、Pb3O4、Pb12O19、PbI2、PbBr2、PbF2At least one of PbS, PbSe and PbTe; the organic solvent comprises ethanol.
As an alternative of the present invention, the manner of applying the radiation absorbing material liquid on the lower electrode layer includes: any one of blade coating, extrusion slit coating, ink-jet printing and screen printing.
As an alternative of the present invention, the substrate includes a substrate and a transistor function layer formed on the substrate, wherein the transistor function layer includes a transistor source electrode electrically connected to the lower electrode layer.
As an alternative of the present invention, the manufacturing method further includes a step of forming an interface layer, where the interface layer includes at least one of a hole transport layer and an electron transport layer, where the hole transport layer is formed between the light conversion layer and the upper electrode layer, and the electron transport layer is formed between the light conversion layer and the lower electrode layer.
As an alternative of the present invention, the electron transport layer may be formed by any one of blade coating, extrusion slit coating, inkjet printing, and screen printing; the hole transport layer may be formed by any one of blade coating, extrusion slit coating, inkjet printing, and screen printing.
As an alternative of the invention, the material of the hole transport layer comprises Se and MoO3The material of the electron transport layer comprises TiO2And AZO.
As an alternative of the present invention, the interface layer includes the hole transport layer, and the material of the upper electrode layer includes at least one of Ag, a, and Mo.
The present invention also provides a flat panel detector structure, comprising:
a substrate;
a lower electrode layer formed on the substrate;
the light conversion layer is formed on the lower electrode layer and comprises a lead-containing material layer, and the lead-containing material layer comprises a lead-containing compound; and
and the upper electrode layer is formed on the light conversion layer.
As an alternative of the invention, the lead-containing compound comprises PbO, PbO2、Pb3O4、Pb12O19、PbI2、PbBr2、PbF2And at least one of PbS, PbSe and PbTe.
As an alternative of the present invention, the substrate includes a substrate and a transistor function layer on the substrate, wherein the transistor function layer includes a transistor source electrode electrically connected to the lower electrode layer.
As an alternative of the present invention, the flat panel detector structure further includes an interface layer, where the interface layer includes at least one of a hole transport layer and an electron transport layer, where the hole transport layer is located between the light conversion layer and the upper electrode layer, and the electron transport layer is located between the light conversion layer and the lower electrode layer.
As an alternative of the invention, the material of the hole transport layer comprises Se and MoO3The material of the electron transport layer comprises TiO2And AZO.
As an alternative of the present invention, the interface layer includes a hole transport layer, and the material of the upper electrode layer includes at least one of Ag, Al, and Mo.
As described above, the flat panel detector structure and the preparation method thereof of the invention improve the material of the existing light conversion layer, improve the ray absorption capacity of the light conversion layer, reduce the thickness of the light conversion layer, improve the imaging quality, simplify the design difficulty of the device, improve the reliability of the device, and reduce the potential safety hazard to operators and patients, and the invention also designs the forming method of the light conversion layer, etc., solves the problems existing in the formation of a polycrystalline structure, improves the chemical composition and phase uniformity of the device, improves the uniformity of images, improves the effective utilization rate of raw materials, improves the preparation speed of material layers, simplifies process equipment, reduces the cost, and in addition, the invention designs the structure of the detector, improves the problem of leakage current, reduces the noise of the detector, improves the sensitivity and contrast of the detector, etc., the electrode material of the detector is improved, and the process cost is reduced.
Drawings
FIG. 1 is a schematic diagram of a process for fabricating a flat panel detector structure according to the present invention.
FIG. 2 is a schematic diagram of a substrate for fabricating a flat panel detector structure according to the present invention.
FIG. 3 is a schematic diagram of a substrate structure in the fabrication of the flat panel detector structure of the present invention.
FIG. 4 is a schematic structural diagram of the formation of the lower electrode layer in the fabrication of the flat panel detector structure of the present invention.
FIG. 5 is a schematic structural diagram of a light conversion layer formed in the fabrication of the flat panel detector structure of the present invention.
FIG. 6 is a schematic structural diagram of an upper electrode layer formed in the fabrication of a flat panel detector structure according to the present invention.
Fig. 7 is a schematic diagram of the structural connection of the flat panel detector according to an exemplary embodiment of the present invention.
Figure 8 shows a comparison of work functions for different materials.
Fig. 9 is a schematic diagram showing an equivalent circuit of a light conversion layer and a TFT layer of a flat panel detector according to an embodiment of the present invention.
Description of the element reference numerals
100 substrate
100a substrate
100b transistor functional layer
101 lower electrode layer
102 light conversion layer
103 upper electrode layer
104 hole transport layer
105 electron transport layer
106 transistor gate
107 transistor source
108 transistor drain
109 photodiode
110 readout line
111 scan line
S1-S4
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 9. It should be noted that the drawings provided in the present embodiment are only schematic and illustrate the basic idea of the present invention, and although the drawings only show the components related to the present invention and are not drawn according to the number, shape and size of the components in actual implementation, the form, quantity and proportion of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
As shown in fig. 1, the present invention provides a method for manufacturing a flat panel detector structure, comprising the following steps:
providing a substrate, and preparing a lower electrode layer on the substrate;
providing ray absorption material liquid, wherein the ray absorption material liquid contains lead element;
coating the radiation absorbing material liquid on the lower electrode layer to prepare a light conversion layer on the lower electrode layer based on the coated radiation absorbing material liquid; and
and preparing an upper electrode layer on the light conversion layer.
The fabrication of the flat panel detector structure of the present invention will be described in detail below with reference to the accompanying drawings.
First, as shown in S1 of fig. 1 and fig. 2-4, a substrate 100 is provided, and a lower electrode layer 101 is prepared on the substrate;
specifically, the substrate 100 is provided to prepare a relevant structural layer in a flat panel detector structure (such as a linear X-ray flat panel detector) on the substrate 100, and the substrate 100 may include a glass substrate, and of course, may further include other functional layers required by the flat panel detector, which are designed according to actual requirements. Next, a lower electrode layer 101 is prepared on the substrate 100, and a material of the lower electrode layer 101 includes, but is not limited to, ITO (indium tin oxide) or Ag, and may be formed by sputtering or evaporation.
As an example, the substrate 100 includes a substrate 100a and a transistor functional layer 100b formed on the substrate 100a, wherein the transistor functional layer 100b includes a transistor source electrically connected to the lower electrode layer 101.
Specifically, as shown in fig. 4, in an example, a structure of a substrate 100 is provided, which includes a substrate 100a and a Transistor functional layer 100b, in this example, the substrate 100a may be a glass substrate, and the Transistor functional layer 100b may be a Thin Film Transistor (TFT) layer, in this example, a Transistor source (see a Transistor source 107 in fig. 9) in the TFT layer (as a switch layer) is electrically connected to the lower electrode layer 101, that is, the lower electrode layer 101 is electrically connected to the light conversion layer 102 for signal transmission, and of course, the Transistor functional layer further includes a Transistor gate and a Transistor drain, and in an example, the Transistor, such as the Transistor source layer and the Transistor drain layer in the TFT layer, and the lower electrode layer share the same material layer.
Next, as shown by S2 in fig. 1, a radiation absorbing material liquid is provided, wherein the radiation absorbing material liquid contains lead element therein, and the radiation absorbing material liquid includes a lead-containing compound liquid. Continuing, as shown in S3 in fig. 1 and fig. 5, the radiation absorbing material liquid is coated on the lower electrode layer 101, so as to prepare a light conversion layer 102 on the lower electrode layer 101 based on the coated radiation absorbing material liquid.
Specifically, a light conversion layer 102 is formed on the lower electrode layer 101, wherein the light conversion layer is also called a conversion layer and can convert high-energy incident X-ray photons into carriers (electron-hole pairs), and in the present invention, the light conversion layer 102 is formed by using the radiation absorbing material liquid containing lead (Pb) element, the atomic number of lead is 82, lead oxide (PbO) is taken as an example, and the density of PbO is 9.53g/cm3Therefore, the film has strong absorption to X-ray, in one example, the thickness of PbO film is only one tenth to one third of that of amorphous Se film under the condition of absorbing X-ray with the same energy, such as: the X-ray energy required by mammary gland detection is 10KeV-30KeV, the thickness of the amorphous selenium film is about 200 μm-500 μm, the X-ray energy used by X-ray chest X-ray is 50KeV-80KeV, and the thickness of the amorphous selenium film is required to reach 800 μm-2000 μm in order to fully absorb the X-ray; however, the PbO film thickness is only 10 μm to 50 μm when the X-ray energy is 10KeV to 30KeV, and 200 μm to 800 μm when the X-ray energy is 50KeV to 80 KeV. That is, the light conversion layer 102 prepared by the radiation absorbing material liquid containing Pb element can significantly improve the radiation absorbing ability of the light conversion layer 102, such as the absorbing ability for X-rays, especially high-energy X-rays, thereby reducing the thickness of the light conversion layer 102 at the same radiation absorbing energy when ensuring the radiation absorption, solving the problem caused by the increase of the film thickness, that is, the problem of the deterioration of the uniformity of the light conversion layer due to the increase of the film thickness, which leads to the deterioration of the imaging quality, and the problem of the increase of the voltage at both ends of the film layer due to the sufficient collection of charges, thereby reducing the design difficulty of the device due to the use of high voltage, reducing the reliability, and reducing the design difficulty of the device due to the use of high voltageThe problems of potential safety hazard and the like are more easily caused to operators and patients.
As an example, the lead-containing compound liquid includes a radiation absorbing material including a lead-containing compound and an organic solvent, and the radiation absorbing material is dissolved in the organic solvent to form the lead-containing compound liquid.
As an example, the lead-containing compound includes PbO, PbO2、Pb3O4、Pb12O19、PbI2、PbBr2、PbF2At least one of PbS, PbSe and PbTe; the organic solvent comprises ethanol.
Specifically, the radiation absorbing material liquid may be a radiation absorbing material solution, or a radiation absorbing material suspension, and in one example, the radiation absorbing material liquid is formed by dissolving (dissolving or uniformly distributing) the radiation absorbing material in the organic solvent, wherein the radiation absorbing material may be a material containing lead element, and in one example, the radiation absorbing material liquid is formed by dissolving a lead-containing compound in the organic solvent, wherein the lead-containing compound may be any one of the above compounds, or a combination of two or more of the above compounds, and in the case of PbO, PbO nanoparticles or quantum dots are dispersed in ethanol and sufficiently stirred to be uniform, so as to form the radiation absorbing material liquid.
As an example, the method of applying the radiation absorbing material liquid on the lower electrode layer 101 includes: blade coating, slot-die coating, ink jet printing, and screen printing.
Specifically, in this example, a method of coating the liquid of the radiation absorbing material to form the light conversion layer 102 is provided, that is, the light conversion layer 102 is manufactured by a solution method (such as blade coating, ink-jet printing, and screen printing), wherein the blade coating may be a method of manually coating with a doctor blade or the like to obtain a material coating with a desired thickness, extrusion slit coating is a method of extruding a solution in a film head onto a substrate surface with a certain pressure, drying after coating, to form a desired material film, ink-jet printing may be a method of absorbing a solution reagent to be sprayed with a nozzle, then moving the solution reagent to the surface of a structure to be processed, spraying a liquid drop onto the surface of the structure to be processed with a motive force of an injector in the form of heat-sensitive or sound-controlled method, to form a material film with a desired thickness, screen printing may be a method of forming a material film with a mesh, the basic principle that the meshes of the non-image-text part cannot penetrate solution reagent is adopted to print, solution (the liquid of the ray absorbing material) is poured into one end of a screen printing plate during printing, a scraper is used for applying certain pressure to the solution part on the screen printing plate, meanwhile, the scraper moves towards the other end of the screen printing plate at a constant speed, the solution is extruded onto a printing stock (the surface of a structure to be processed, such as the surface of the lower electrode layer) from the meshes of the image-text part by the scraper during moving, and the solution processing has the following advantages: the solution method may use an amorphous radiation absorbing material such as amorphous PbO quantum dots or nanoparticles, which do not have grain boundaries, and may avoid the above-described various problems caused by grain boundaries; the film with uniform thickness can be obtained by processing with the solution method, the defects of nonuniform longitudinal chemical formula, nonuniform thickness and the like of the film are avoided, the film is integrally formed by the solution method, the chemical composition and the phase of the film including the bottom and the top are uniform, and the uniformity of formed images can be improved; the solution method has high material utilization rate (close to 100 percent) and high speed, and can not cause waste; the solution method does not need to use plasma and high vacuum equipment, all processes can be carried out in the atmospheric atmosphere, the construction cost of a production line is effectively reduced, namely, an amorphous structure can be formed by the solution method, the defect of a light conversion layer forming a polycrystalline structure is overcome, the polycrystalline structure has obvious crystal boundaries, the generation of the crystal boundaries can cause the migration of carriers (electrons or holes) to be blocked, the collection of the carriers is incomplete, the contrast of an image is influenced, the existence of the crystal boundaries can cause the carriers to be gathered at the crystal boundaries, the carriers can not be completely collected at a current frame (such as a first frame) and can be released under the action of room temperature when a next frame (such as a second frame) is read, the ghost (ghesting) of the previous frame (first frame) exists in the ghost of an image of the second frame, the compactness of a film layer can be reduced, the compactness is reduced, and the X-ray absorption capacity is reduced, to achieve the same absorption capacity, the film thickness needs to be increased, and the increase of the film thickness causes the carrier (electron or hole) not to be transmitted to the electrode, thereby causing the deterioration of the read signal and the reduction of the image contrast; if contrast is to be increased, voltage must be increased to fully collect carriers, and increasing operating voltage will greatly increase dark current (dark current) and cause a decrease in device responsivity, and excessively high dark current causes the device to be unresponsive to X-rays (because X-ray generated photogenerated carriers are covered by background noise).
Finally, as shown in S4 in fig. 1 and fig. 6, an upper electrode layer 103 is prepared on the light conversion layer 102.
Specifically, the upper electrode layer 103 is formed on the light conversion layer 102 by evaporation, wherein the material of the upper electrode layer 103 can be selected according to the actual situation, so as to implement the operation of the detector. In addition, the steps for preparing the detector structure can be carried out in an exchange step mode, and the process implementation can be carried out according to the actual exchange step sequence.
As an example, the preparation method further includes a step of forming an interface layer, the interface layer includes at least one of a hole transport layer 104 and an electron transport layer 105, the hole transport layer 104 is formed between the light conversion layer 102 and the upper electrode layer 103, and the electron transport layer 105 is formed between the light conversion layer 102 and the lower electrode layer 101.
Specifically, as shown in fig. 7, in one example, the interface layer is introduced between the light conversion layer 102 and the upper and lower electrode layers, the hole transport layer 104 may be introduced only between the light conversion layer 102 and the upper electrode layer 103, the electron transport layer 105 may be introduced only between the light conversion layer 102 and the lower electrode layer 101, or both the hole transport layer 104 and the electron transport layer 105 may be introduced between the light conversion layer 102 and the upper electrode layer 103 and between the light conversion layer 102 and the lower electrode layer 101.
As examples, the material of the hole transport layer 104 includes Se and MoO3At least one of, the material package of the electron transport layer 105Comprises TiO2And AZO (ZnO: Al, aluminum-doped zinc oxide).
As an example, the interface layer includes the hole transport layer 104, and the material of the upper electrode layer 103 includes at least one of Ag, Al, and Mo.
Specifically, for the hole transport layer 104, that is, the electron blocking layer, it is possible to achieve the transport of carrier holes and simultaneously block the transport of electrons, and further, in an example, the presence of the hole transport layer 104 may also reduce the work function at the interface of the light conversion layer, so that the material of the upper electrode layer may be improved, and cheap silver, aluminum or molybdenum may be used, so as to avoid the use of expensive elements and reduce the cost, and in an example, the material of the hole transport layer 104 is selected from Se and MoO3At least one of the layers may be a Se layer or a MoO layer3The layer, or both, may be a stacked structure, taking Se layer as an example, and referring to fig. 8, the hole transport can only occur in the valence band, taking the lead-containing compound as PbO as an example, it can be seen that the peak of the valence band (valence band top) of PbO is-5.2 eV, the work function of Ag (Ag is metal, it is considered that the conduction band and the valence band are mixed, and therefore, the horizontal line in the figure) is-4.5 eV, if the hole is to be directly transported from PbO to Ag electrode, the hole needs to overcome the potential barrier (energy difference) of 0.7eV, which is too large to transport the hole to Ag electrode. While the work function of the gold element is about-5.0 eV (not marked in the figure), holes are transmitted to the gold (Au) electrode from the PbO valence band, and only the potential barrier of 0.2eV needs to be overcome. Therefore, when PbO is directly in contact with a metal material (electrode), only a metal material having a high work function (e.g., noble metal such as gold, rhodium, platinum, etc.) can be selected as an electrode material. However, in one example, as can be seen from the work function diagram shown in fig. 8, the hole transport layer 104 may select: se or MoO3Taking the Se layer as an example, the valence band top of Se is-4.8 eV, if a Se element layer is inserted between PbO and Ag, holes are firstly transmitted from PbO to Se (barrier is 0.4eV), and then holes are transmitted from the valence band top of Se to Ag electrode (barrier is 0.3eV), so that Se acts as a bridge to enable the holes to be transmitted to Ag electrode, which can be generally called workThe functional modification, i.e. phase change, reduces the work function of PbO, and likewise, MoO3The same function as the hole transport layer.
In addition, the electron transport layer 105 can also have the functions of lowering the work function and blocking hole-transporting electrons, in one example, the material of the lower electrode layer is selected to be Ag or Al, the electron transport can only be performed in the conduction band, the conduction band position of PbO is-3.0 eV, the lower electrode layer generally uses the source (source) or drain (drain) of TFT, the material of the lower electrode layer is Ag or Al, as can be seen from the power function diagram in fig. 8, the conduction band position of PbO (-3.0eV) is higher than the Ag work function (-4.5eV), and the electron can be easily transited from the high-energy PbO conduction band directly to the Ag electrode, so the purpose of the electron transport layer in this example is to block holes from entering the lower electrode layer, thereby increasing the quantum efficiency (conversion efficiency) and reducing the dark current.
As an example, a manner of forming the electron transport layer 105 includes any one of blade coating, slot-die coating (slot-die), inkjet printing, and screen printing; the hole transport layer 104 may be formed by any one of knife coating, slot-die coating (slot-die), inkjet printing, and screen printing.
Specifically, the hole transport layer 104 and the electron transport layer 105 may be formed by a solution method, such as knife coating, slot-die coating, ink jet printing, or screen printing.
To further illustrate the process of the present invention for fabricating a probe structure based on a solution method, an example is provided, which includes the steps of: 1) adding TiO into the mixture2Or dispersing AZO quantum dots or nano particles in ethanol, and fully and uniformly stirring; 2) coating the TFT substrate (prepared transistor function layer) by a solution method to form an electron transport layer, wherein the electron transport layer is prepared from the nano material/quantum dot dispersion liquid, and the thickness of the film layer is 1000nm-3000 nm; 3) after the film layer is coated, the film layer is placed in a drying oven at 100 ℃ for fully drying, for example, drying for 5 minutes; 4) dispersing PbO nano particles or quantum dots in ethanol, and fully and uniformly stirring; 5) coating the solution on the electron transport layerForming a PbO light conversion layer with the thickness of 50-800 μm; 6) after the film layer is coated, the film layer is placed in a drying oven at 100 ℃ for fully drying, for example, drying for 5 minutes; 7) adding Se or MoO3Dispersing the quantum dots or the nano particles in ethanol, and fully and uniformly stirring; 8) coating a hole transport layer on the PbO light conversion layer, wherein the hole transport layer is made of Se or MoO3The thickness of the film layer of the dispersion liquid is 1000nm-3000 nm; 9) after the film layer is coated, the film layer is placed in a drying oven at 100 ℃ for fully drying, for example, drying for 5 minutes; 10) and depositing an Ag or Al electrode on the hole transport layer by evaporation. Therefore, by implementing the scheme, the amorphous PbO is used to avoid image ghost (ghost), the solution method is used for simple process, high vacuum equipment and plasma equipment are not needed, the process cost is low, the interface layer is used to reduce the leakage current and improve the sensitivity of the detector and the contrast of the final image, the interface layer is used to adjust the work function, so that the upper electrode can use cheaper silver or aluminum, the use of expensive gold elements is avoided, and the cost is effectively reduced.
In addition, as shown in fig. 6-9 and referring to fig. 1-5, the present invention also provides a flat panel detector structure comprising:
a substrate 100;
a lower electrode layer 101 formed on the substrate 100;
a light conversion layer 102 formed on the lower electrode layer 101, wherein the light conversion layer 102 contains lead element, the light conversion layer includes a lead-containing material layer, and the lead-containing material layer includes a lead-containing compound; and
and an upper electrode layer 103 formed on the light conversion layer 102.
Specifically, the flat panel detector structure of the present invention includes a substrate 100, and the substrate 100 may be used to prepare a related structural layer in the flat panel detector structure (such as a linear X-ray flat panel detector), wherein the substrate 100 may include a glass substrate, and of course, may also include other functional layers required by the flat panel detector, and is designed according to actual requirements. In addition, the lower electrode layer 101 is formed on the substrate 100, and the material of the lower electrode layer 101 may be, but is not limited to, ITO (indium tin oxide) or Ag.
As an example, the substrate 100 includes a substrate 100a and a transistor functional layer 100b on the substrate, wherein the transistor functional layer 100b includes a transistor source electrically connected to the lower electrode layer 101.
In an example, the substrate 100 includes a substrate 100a and a Transistor functional layer 100b, in this example, the substrate 100a may be a glass substrate, and the Transistor functional layer 100b may be a Thin Film Transistor (TFT) layer, in this example, a Transistor source (source) in the TFT layer (as a switch layer) is electrically connected to the lower electrode layer 101, that is, the lower electrode layer 101 is electrically connected to the light conversion layer 102 for signal transmission, and in this example, the Transistor functional layer may be a Transistor source layer and a Transistor drain layer in the TFT layer, which share the same material layer with the lower electrode layer.
As an example, the lead-containing compound includes PbO, PbO2、Pb3O4、Pb12O19、PbI2、PbBr2、PbF2And at least one of PbS, PbSe and PbTe.
Specifically, for the light conversion layer 102, the light conversion layer is also called a conversion layer, and can convert high-energy incident X-ray photons into carriers (electron-hole pairs), in the present invention, the light conversion layer 102 contains lead element, the atomic number of lead is 82, lead oxide (PbO) is taken as an example, and the density of PbO is 9.53g/cm3Therefore, the film has strong absorption to X-ray, in one example, the thickness of PbO film is only one tenth to one third of that of amorphous Se film under the condition of absorbing X-ray with the same energy, such as: the X-ray energy required by mammary gland detection is 10KeV-30KeV, the thickness of the amorphous selenium film is about 200 μm-500 μm, the X-ray energy used by X-ray chest X-ray is 50KeV-80KeV, and the thickness of the amorphous selenium film is required to reach 800 μm-2000 μm in order to fully absorb the X-ray; however, the PbO film thickness is only 10 μm to 50 μm when the X-ray energy is 10KeV to 30KeV, and 200 μm to 800 μm when the X-ray energy is 50KeV to 80 KeV. That is, the radiation absorbing material liquid containing Pb elementThe prepared light conversion layer 102 can remarkably improve the ray absorption capacity of the light conversion layer 102, such as the absorption capacity for X rays, particularly high-energy X rays, so that the film thickness of the light conversion layer 102 under the same ray absorption energy when ensuring ray absorption is reduced, the problem caused by the increase of the film thickness is solved, namely, the problem that the uniformity of the light conversion layer is deteriorated due to the increase of the film thickness to cause the deterioration of imaging quality is solved, the problem that the voltage at two ends of the film is increased due to the sufficient collection of charges is reduced, and the problems that the design difficulty of devices is increased, the reliability is reduced due to the use of high voltage, potential safety hazards are more easily caused to operators and patients and the like are solved.
Specifically, the light conversion layer 102 may be a lead-containing material layer containing a lead-containing compound so that the light conversion layer contains the lead element, for example, in an example, the formation of the light conversion layer 102 includes formation using a radiation absorbing material liquid, further, the raw material for forming the radiation absorbing material liquid includes a radiation absorbing material and an organic solvent, the radiation absorbing material liquid is formed by dissolving the radiation absorbing material in the organic solvent, wherein the radiation absorbing material may be a material containing the lead element, such as a lead-containing compound, in an example, the radiation absorbing material liquid is formed by dissolving a lead-containing compound in an organic solvent, the lead-containing compound may be any one of the above compounds, or a combination of two or more of the above compounds, taking PbO as an example, PbO nano-particles or quantum dots are dispersed in ethanol and are fully and uniformly stirred to form the ray absorption material liquid.
As an example, the flat panel detector structure further includes an interface layer including at least one of a hole transport layer 104 and an electron transport layer 105, wherein the hole transport layer 104 is located between the light conversion layer 102 and the upper electrode layer 103, and the electron transport layer 105 is located between the light conversion layer 102 and the lower electrode layer 101.
Specifically, as shown in fig. 7, in one example, the interface layer is introduced between the light conversion layer 102 and the upper and lower electrode layers, the hole transport layer 104 may be introduced only between the light conversion layer 102 and the upper electrode layer 103, the electron transport layer 105 may be introduced only between the light conversion layer 102 and the lower electrode layer 101, or both the hole transport layer 104 and the electron transport layer 105 may be introduced between the light conversion layer 102 and the upper electrode layer 103 and between the light conversion layer 102 and the lower electrode layer 101.
As examples, the material of the hole transport layer 104 includes Se and MoO3The material of the electron transport layer 105 includes TiO2And AZO.
As an example, the interface layer includes a hole transport layer 104, and the material of the upper electrode layer 103 includes at least one of Ag, Al, and Mo.
Specifically, for the hole transport layer 104, that is, the electron blocking layer, it is able to achieve the transport of carrier holes and simultaneously block the transport of electrons, and further, in an example, the presence of the hole transport layer 104 can also reduce the work function at the interface of the light conversion layer, so that the material of the upper electrode layer can be improved, and cheap silver and aluminum can be used, and expensive elements can be avoided, so as to reduce the cost, and in an example, the material of the hole transport layer 104 is selected from Se and MoO3At least one of the layers may be a Se layer or a MoO layer3The layer, or both, may be a stacked structure, taking Se layer as an example, and referring to fig. 8, the hole transport can only occur in the valence band, taking the lead-containing compound as PbO as an example, it can be seen that the peak of the valence band (valence band top) of PbO is-5.2 eV, the work function of Ag (Ag is metal, it is considered that the conduction band and the valence band are mixed, and therefore, the horizontal line in the figure) is-4.5 eV, if the hole is to be directly transported from PbO to Ag electrode, the hole needs to overcome the potential barrier (energy difference) of 0.7eV, which is too large to transport the hole to Ag electrode. While the work function of the gold element is about-5.0 eV (not marked in the figure), holes are transmitted to the gold (Au) electrode from the PbO valence band, and only the potential barrier of 0.2eV needs to be overcome. So that when PbO is directly contacted with the metal material (electrode)In this case, only metal materials having a high work function (e.g., noble metals such as gold, rhodium, and platinum) can be selected as the electrode material. However, in one example, as can be seen from the work function diagram shown in fig. 8, the hole transport layer 104 may select: se or MoO3Taking the Se layer as an example, the valence top of Se is-4.8 eV, if a Se element layer is inserted between PbO and Ag electrode, holes are first transported from PbO to Se (barrier 0.4eV), and then transported from the valence top of Se to Ag electrode (barrier 0.3eV), so that Se acts as a bridge to transport holes to Ag electrode, which can be generally called work function modification, i.e. phase-change lowering of the work function of PbO, and similarly, MoO3The same function as the hole transport layer.
In addition, the electron transport layer 105 may also have the functions of lowering the work function and blocking hole-transporting electrons, in an example, the material of the lower electrode layer is selected to be Ag or Al, the electron transport can only be performed in the conduction band, the conduction band position of PbO is-3.0 eV, the lower electrode layer generally uses the source (source) or drain (drain) of the TFT, the material of the lower electrode layer is Ag or Al, as can be seen from the work function diagram in fig. 8, the conduction band position of PbO (-3.0eV) is higher than the Ag work function (-4.5eV), and the electron can be easily transited from the high-energy PbO conduction band directly to the Ag electrode, so the purpose of the electron transport layer in this example is to block the hole from entering the lower electrode layer.
In addition, as shown in fig. 7 and 9, the operation process of the flat panel detector in an example provided by the present invention is as follows: the upper electrode layer 103 of the device is connected with the negative electrode (common electrode, Vcom) of a direct current power supply, the lower electrode layer 105 is electrically connected with the positive electrode of the power supply, and the electric field intensity is 1 to 5V/um; in the absence of external X-ray, electrons and holes are depleted in the light conversion layer 102 (e.g., PbO layer), and theoretically no current is generated; when the device receives X-ray exposure (as shown in fig. 7), X-ray photons ionize the PbO material, generating photogenerated carriers (electron-hole pairs); under the action of an electric field, the holes drift towards the upper electrode layer, and the electrons drift towards the lower electrode layer; however, a small amount of electrons drift toward the upper electrode, and a small amount of holes drift toward the lower electrode; because the hole transmission layer is arranged between the upper electrode layer and the PbO layer, only holes can be transmitted to the upper electrode layer, and electrons are completely blocked at the interface layer; similarly, there is an electron transport layer between the lower electrode layer and the PbO, so only electrons can be transported to the lower electrode layer, and holes are blocked by the electron transport layer; since the lower electrode of the PbO photodiode 109 (i.e., the light conversion layer) is connected to the TFT source (source), i.e., the transistor source 107, electrons are transmitted to the lower electrode layer, then transmitted to the TFT source, and stored in the TFT source; when the TFT is turned on (when the voltage of the gate electrode 106 of the transistor is greater than the threshold voltage of the TFT, the TFT is in an on state, and the source electrode 107 and the drain electrode 108 of the transistor are turned on), electrons are transferred from the source electrode of the transistor to the drain electrode (drain) of the transistor, and then transferred to the "readout line 110" and read by an external circuit.
In summary, the present invention provides a flat panel detector structure and a method for manufacturing the same, wherein the method comprises: providing a substrate, and preparing a lower electrode layer on the substrate; providing a radiation absorbing material liquid, wherein the radiation absorbing material liquid includes a lead-containing compound liquid; coating the radiation absorbing material liquid on the lower electrode layer to prepare a light conversion layer on the lower electrode layer based on the coated radiation absorbing material liquid; and preparing an upper electrode layer on the light conversion layer. Through the scheme, the flat panel detector structure and the preparation method thereof improve the material of the existing light conversion layer, improve the ray absorption capacity of the light conversion layer, reduce the thickness of the light conversion layer, improve the imaging quality, simplify the design difficulty of the device, improve the reliability of the device, and reduce the potential safety hazard to operators and patients, and the invention also designs the forming method of the light conversion layer and the like, solves the problems existing in the formation of a polycrystalline structure, improves the chemical composition and phase uniformity of the device, improves the uniformity of images, improves the effective utilization rate of raw materials, improves the preparation speed of material layers, simplifies process equipment, reduces the cost, and in addition, the invention designs the structure of the detector, improves the problem of leakage current, reduces the noise of the detector, improves the sensitivity, the contrast and the like of the detector, the electrode material of the detector is improved, and the process cost is reduced. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (13)
1. A method for manufacturing a flat panel detector structure is characterized by comprising the following steps:
providing a substrate, and preparing a lower electrode layer on the substrate;
providing a radiation absorbing material liquid, wherein the radiation absorbing material liquid includes a lead-containing compound liquid;
coating the radiation absorbing material liquid on the lower electrode layer to prepare a light conversion layer on the lower electrode layer based on the coated radiation absorbing material liquid;
the light conversion layer comprises a PbO film layer; the thickness of the PbO film layer is 50-800 μm;
and
preparing an upper electrode layer on the light conversion layer, wherein the material of the upper electrode layer comprises at least one of Ag, Al and Mo;
the preparation method also comprises a step of forming an interface layer, wherein the interface layer comprises a hole transport layer, and the hole transport layer is formed between the light conversion layer and the upper electrode layer;
the hole transportThe material of the layer comprises Se and MoO3At least one of (1).
2. The method for manufacturing a flat panel detector structure according to claim 1, wherein the lead-containing compound liquid comprises a radiation absorbing material and an organic solvent, wherein the radiation absorbing material comprises a lead-containing compound, and the radiation absorbing material is dissolved in the organic solvent to form the lead-containing compound liquid.
3. The method of claim 2, wherein the lead-containing compound further comprises PbO2、Pb3O4、Pb12O19、PbI2、PbBr2、PbF2At least one of PbS, PbSe and PbTe; the organic solvent comprises ethanol.
4. The method for preparing a flat panel detector structure according to claim 1, wherein the step of applying the radiation absorbing material liquid on the lower electrode layer comprises: any one of blade coating, extrusion slit coating, ink-jet printing and screen printing.
5. The method of claim 1, wherein the substrate comprises a substrate and a transistor functional layer formed on the substrate, wherein the transistor functional layer comprises a transistor source electrically connected to the lower electrode layer.
6. The method for manufacturing a flat panel detector structure according to any of claims 1-5, wherein the interface layer comprises an electron transport layer formed between the light conversion layer and the lower electrode layer.
7. The method for manufacturing the flat panel detector structure according to claim 6, wherein the electron transport layer is formed by any one of blade coating, extrusion slit coating, ink-jet printing and screen printing; the hole transport layer may be formed by any one of blade coating, extrusion slit coating, inkjet printing, and screen printing.
8. The method of claim 6, wherein the electron transport layer comprises TiO2And AZO.
9. A flat panel detector structure, comprising:
a substrate;
a lower electrode layer formed on the substrate;
the light conversion layer is formed on the lower electrode layer and comprises a lead-containing material layer, and the lead-containing material layer comprises a lead-containing compound;
the light conversion layer comprises a PbO film layer; the thickness of the PbO film layer is 50-800 μm;
and
the upper electrode layer is formed on the light conversion layer, and the material of the upper electrode layer comprises at least one of Ag, Al and Mo;
the flat panel detector structure further comprises an interface layer, wherein the interface layer comprises a hole transport layer, and the hole transport layer is positioned between the light conversion layer and the upper electrode layer;
the material of the hole transport layer is selected from Se and MoO3At least one of (1).
10. The flat panel detector structure of claim 9, wherein the lead-containing compound further comprises PbO2、Pb3O4、Pb12O19、PbI2、PbBr2、PbF2And at least one of PbS, PbSe and PbTe.
11. The flat panel detector structure of claim 9, wherein the base comprises a substrate and a transistor functional layer on the substrate, wherein the transistor functional layer comprises a transistor source electrically connected to the lower electrode layer.
12. A flat panel detector structure according to any of claims 9-11, characterized in that the interface layer further comprises an electron transport layer, which is located between the light conversion layer and the lower electrode layer.
13. The flat panel detector structure of claim 12, wherein the material of the electron transport layer comprises TiO2And AZO.
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| CN104218045A (en) * | 2013-06-05 | 2014-12-17 | 朱兴华 | Digital X-ray flat panel detector based on lead iodide photoconductive layer |
| CN104362187A (en) * | 2014-10-27 | 2015-02-18 | 中国科学院上海硅酸盐研究所 | Lead iodide and lead oxide compound film and production method thereof |
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