WO2022104705A1 - 一种全无机晶体管型x射线探测器及其制备方法 - Google Patents

一种全无机晶体管型x射线探测器及其制备方法 Download PDF

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WO2022104705A1
WO2022104705A1 PCT/CN2020/130452 CN2020130452W WO2022104705A1 WO 2022104705 A1 WO2022104705 A1 WO 2022104705A1 CN 2020130452 W CN2020130452 W CN 2020130452W WO 2022104705 A1 WO2022104705 A1 WO 2022104705A1
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layer
electrode
ray
channel semiconductor
gate insulating
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李佳
曹勇
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/20—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
    • H10F30/29—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to radiation having very short wavelengths, e.g. X-rays, gamma-rays or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/20—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
    • H10F30/29—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to radiation having very short wavelengths, e.g. X-rays, gamma-rays or corpuscular radiation
    • H10F30/298—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to radiation having very short wavelengths, e.g. X-rays, gamma-rays or corpuscular radiation the devices being characterised by field-effect operation, e.g. MIS type detectors

Definitions

  • the invention relates to the technical field of X-ray detectors, in particular to an all-inorganic transistor type X-ray detector and a preparation method thereof.
  • amorphous selenium flat panel detectors are usually based on amorphous selenium (a-Se). Requirements for radiography ( ⁇ 20keV).
  • a-Se amorphous selenium flat-panel X-ray detector
  • the amorphous selenium flat-panel X-ray detector has a two-terminal structure and does not have a charge gain function, so it does not have a signal amplification function, resulting in a low signal-to-noise ratio.
  • X-ray direct detectors are usually integrated with field effect transistors, and transistors are used to amplify the electrical signal.
  • top electrode on the X-ray absorption layer, and apply a bias voltage on the top electrode, so that the electron holes generated by the X-ray irradiation are separated, and carriers are injected into the conductive communication.
  • a top electrode is required for typical detector structures, such as patent applications CN201811094472.2, CN201810563401.6CN201710977868.0, etc. Since this type of detector structure requires additional electrodes, it is not conducive to simplifying the fabrication process.
  • the purpose of the present invention is to overcome the above-mentioned defects of the prior art, and to provide an all-inorganic transistor-type X-ray detector and a preparation method thereof. work under.
  • an all-inorganic transistor type X-ray detector includes a substrate, a gate electrode, a gate insulating layer, a channel semiconductor layer, a source electrode and a drain electrode, an X-ray absorption layer and a protective layer, wherein the X-ray absorption layer and the channel semiconductor layer are formed
  • a heterojunction that, upon X-ray irradiation, separates generated electron-hole pairs and allows carriers generated by the X-ray absorbing layer to be injected into the channel semiconductor layer.
  • the gate electrode is formed on the substrate; the gate insulating layer is formed on the gate electrode; the source electrode and the drain electrode are respectively formed on the gate insulating layer; The channel semiconductor layer is formed on the gate insulating layer, the drain electrode and the source electrode; the X-ray absorption layer is formed and covers the channel semiconductor layer.
  • the lower surface of the gate electrode is connected to the substrate; the upper surface of the gate electrode is connected to the lower surface of the gate insulating layer; the upper surface of the gate insulating layer is connected to the trench
  • the lower surface of the channel semiconductor layer is connected; the lower surface of the source electrode and the lower surface of the drain electrode are connected to the upper surface of the channel semiconductor layer; the upper surface of the source electrode and the upper surface of the drain electrode are respectively connected to the upper surface of the channel semiconductor layer.
  • the lower surface of the X-ray absorption layer is connected; the upper surface of the X-ray absorption layer is connected with the protective layer.
  • the detector provided by the present invention further includes a charge transport layer, wherein the gate electrode is formed on the substrate; the gate insulating layer is formed on the gate electrode; the source electrode and The drain electrodes are respectively formed on the gate insulating layer; the channel semiconductor layer is formed on the gate insulating layer, the drain electrode and the source electrode; the charge transport layer is formed and covers the on the channel semiconductor layer; the X-ray absorption layer is formed and covered on the charge transport layer.
  • the lower surface of the gate electrode is connected to the substrate, the upper surface of the gate electrode is connected to the lower surface of the gate insulating layer; the lower surface of the source electrode and the lower surface of the drain electrode in contact with the gate insulating layer, the channel semiconductor layer covers the drain electrode, the source electrode and the gate insulating layer; the channel semiconductor layer is connected to the lower surface of the X-ray absorption layer ; The upper surface of the X-ray absorbing layer is connected with the protective layer.
  • the X-ray absorption layer is formed on the substrate; the source electrode and the drain electrode are respectively formed on the X-ray absorption layer; the channel semiconductor layer is formed and covered on on the X-ray absorption layer, the drain electrode and the source electrode; the gate insulating layer is formed on the channel semiconductor; the gate electrode is formed on the gate insulating layer; the protective layer is formed on the gate electrode.
  • the gate electrode, the drain electrode and the source electrode are made of gold, silver, copper, aluminum, molybdenum, nickel, indium tin oxide, indium tin oxide, indium zinc oxide, transparent conductive plastic, conductive compound, heavy doped One or more of hetero semiconductor materials.
  • the channel semiconductor layer is made of one or more semiconductor materials such as amorphous silicon, single crystal silicon, polycrystalline silicon, tin oxide, zinc oxide, indium gallium zinc oxide, molybdenum disulfide, lead iodide, etc. production.
  • semiconductor materials such as amorphous silicon, single crystal silicon, polycrystalline silicon, tin oxide, zinc oxide, indium gallium zinc oxide, molybdenum disulfide, lead iodide, etc. production.
  • the X-ray absorbing layer comprises amorphous selenium, lead oxide, lead sulfide, mercury iodide, methylammonium lead iodide, antimony zinc cadmium, cesium lead iodide, cesium lead bromide or mixed cation/anion inorganic One or more of halide perovskites.
  • a method for preparing an all-inorganic transistor type X-ray detector comprising: preparing a gate electrode on a substrate; preparing a gate insulating layer on the substrate and the gate electrode; A channel semiconductor layer is prepared on the gate insulating layer; a source electrode and a drain electrode are prepared on the channel semiconductor layer; an X-ray absorption layer is prepared on the channel semiconductor layer; a protection covering the entire upper surface of the detector is prepared Floor.
  • the present invention has the advantage that no top electrode is required, the unbalanced carriers of the absorption layer are transferred into the transistor channel through the heterojunction interface, and the invention can work under low voltage conditions.
  • the device of the invention has a simple structure, is easy to manufacture, and can save energy during use.
  • FIG. 1 is a schematic structural diagram of a typical detector in the prior art
  • FIG. 2 is a schematic diagram of an X-ray detector with a bottom gate bottom contacting no charge transport layer according to an embodiment of the present invention
  • FIG. 3 is a schematic diagram of an X-ray detector with a bottom gate bottom contacting a charge transport layer according to an embodiment of the present invention
  • FIG. 4 is a schematic diagram of an X-ray detector without a charge transport layer with top grid top contact according to an embodiment of the present invention
  • Fig. 5 is the equivalent circuit diagram of the photoelectron injection type X-ray detector
  • FIG. 6 is a schematic diagram of the transfer curve of the X-ray detector under the condition of adding X-ray irradiation and without adding X-ray according to an embodiment of the present invention.
  • the principle of the all-inorganic transistor-type X-ray detector provided by the present invention is as follows: using the heterojunction formed between the X-ray absorption layer and the channel layer (or called the channel semiconductor layer), the electrons/electrons generated by X-ray irradiation are directly Holes are injected into the channel layer. Due to the injection of carriers, the current between the drain electrode and the source electrode is significantly increased or the threshold voltage of the TFT (thin film transistor) is shifted, thereby realizing the detection of X-rays.
  • the X-ray detector specifically includes: a substrate 101 ; a gate electrode 102 , which is formed on the substrate 101 ; a gate insulating layer (or a dielectric layer) X
  • the ray absorbing layer 105 is formed and covers the channel semiconductor layer 104 .
  • the X-ray detector specifically includes: a substrate 101 ; a gate electrode 102 , which is formed on the substrate 101 ; and a gate insulating layer 103 , which is formed on the gate electrode 102 .
  • source electrode 106 and drain electrode 107 respectively formed on the gate insulating layer 103; channel semiconductor layer 104, formed on the gate insulating layer 103, drain electrode 107 and source electrode 106; charge transport layer 108, formed and covered on On the channel semiconductor layer 104 ; the X-ray absorption layer 105 is formed and covered on the charge transport layer 108 .
  • the X-ray detector specifically includes: a substrate 101; an X-ray absorption layer 105 formed on the substrate 101; a source electrode 106 and a drain electrode 107, are respectively formed on the X-ray absorption layer 105; the channel semiconductor layer 104 is formed and covered on the X-ray absorption layer 105, the drain electrode 107 and the source electrode 106; the gate insulating layer 103 is formed on the channel semiconductor layer 104; The electrode 102 is formed on the gate insulating layer 103; the protective layer (not shown) is formed on the gate electrode 102;
  • the provided transistor-type X-ray detector is based on the principle that the X-ray absorption layer generates unbalanced carriers, and the heterojunction formed by the absorption layer, the charge transport layer and the channel semiconductor layer acts as a In this way, the electron-hole pairs generated when the device is irradiated by X-rays are rapidly separated, and carriers are injected into the channel layer, so that the carrier concentration in the channel layer increases, effectively increasing the photocurrent, The photoelectric properties of the X-ray detection device are improved, thereby improving the sensitivity of the photoelectron injection type X-ray detection device. In particular, when the channel semiconductor layer is prepared by using a semiconductor material with high mobility, the response speed of the detector is effectively increased.
  • the gate electrode 102, the drain electrode 107 and the source electrode 106 are made of any of gold, silver, copper, aluminum, molybdenum, nickel, indium tin oxide, indium zinc oxide, transparent conductive plastics, conductive compounds, and heavily doped semiconductor materials. one or more.
  • the channel semiconductor layer 104 is made of one or more semiconductor materials such as amorphous silicon, single crystal silicon, polycrystalline silicon, tin oxide, zinc oxide, indium gallium zinc oxide, molybdenum disulfide, and lead iodide.
  • semiconductor materials such as amorphous silicon, single crystal silicon, polycrystalline silicon, tin oxide, zinc oxide, indium gallium zinc oxide, molybdenum disulfide, and lead iodide.
  • the material of the X-ray absorbing layer 105 contains amorphous selenium, lead oxide, lead sulfide, mercury iodide, methylammonium lead iodide, antimony zinc cadmium (CZT), cesium lead iodine, cesium lead bromide or mixed cation/ Any one or more of anionic inorganic halide perovskites.
  • an all-inorganic transistor-type X-ray detector that is, a preparation method of a photoelectron injection-type X-ray direct detector based on a heterojunction, taking the transistor-type X-ray detector of FIG. 2 as an example , which forms a built-in electric field through the heterojunction established by the absorption layer and the channel layer, which makes the electron-hole pairs generated by the X-ray acting on the absorption layer rapidly separate, so that the carriers are injected into the channel by the built-in electric field. in the semiconductor layer.
  • the photocurrent can be effectively increased, the photoelectric characteristics of the transistor-type X-ray detection device can be improved, and the sensitivity of X-rays can be enhanced.
  • the present invention since the material selected for the channel semiconductor layer has a larger mobility, the present invention has a faster response speed. And this structure has the functions of switch, amplifier, sensor and capacitor at the same time.
  • the lower surface of the gate electrode 102 is connected to the substrate 101, the upper surface of the gate electrode 102 is connected to the lower surface of the gate insulating layer 103; the upper surface of the gate insulating layer 103 is connected to the channel semiconductor layer
  • the lower surface of the source electrode 106 and the lower surface of the drain electrode 107 are connected to the upper surface of the channel semiconductor layer 104; the upper surface of the source electrode 106 and the upper surface of the drain electrode 107 are respectively connected with the X-ray absorption layer 105
  • the lower surface is connected, and the upper surface of the X-ray absorbing layer 105 is connected to a protective layer (not shown).
  • the gate insulating layer 103 covers the gate electrode 102 and the substrate 101 , and the substrate 101 can be selected from a single crystal silicon wafer, glass or plastic material or the like.
  • the material of the channel semiconductor layer 104 is one or more of single crystal silicon, polycrystalline silicon, indium gallium zinc oxide, zinc oxide, tin oxide, halogen perovskite thin film materials, and the like.
  • the material of the X-ray absorption layer 105 is any one or more of X-ray detection materials including amorphous selenium, lead oxide, mercury iodide, methylammonium lead iodide, antimony zinc cadmium (CZT) or perovskite. kind.
  • the carrier concentration of the X-ray absorbing layer varies with the X-ray dose.
  • the gate electrode 102 is made of any one or more materials selected from aluminum, molybdenum, chromium, titanium, nickel, metal, and indium tin oxide, indium zinc oxide, transparent conductive plastic or conductive glass.
  • the source electrode 106 and the drain electrode 107 are made of any one or more of materials such as aluminum, molybdenum, chromium, titanium, and nickel.
  • the gate electrode 102, the source electrode 106 and the drain electrode 107 are all made of high-conductivity materials.
  • FIG. 5 is an equivalent circuit diagram of a photoelectron injection type X-ray detector, in which D represents a drain electrode, G represents a gate electrode, and S represents a source electrode. It can be seen that the present invention can be equivalent to an integrated device of a diode and a thin film transistor formed between the X-ray light absorption layer and the channel layer. When X-rays are irradiated, the carrier concentration in the absorption layer will increase, and electrons will be injected into the conductive channel of the thin-film transistor under the action of the built-in electric field of the heterojunction, changing the current of the thin-film transistor and acting as X-ray. use of ray sensors.
  • the detection device of the present invention When an appropriate gate bias voltage is applied to the gate electrode and the source electrode, and the output current of the thin film transistor device is less than a certain value, the detection device of the present invention is in an off state; when the output current is greater than or equal to a certain value, the detection device of the present invention is in a state of being turned off. In the open state, it can act as a switch. For example, in an actual circuit, it can be set that when the output current of the thin film transistor device is less than 1nA, the thin film transistor device is in an off state, and when the output current of the thin film transistor device is greater than or equal to 1nA, the thin film transistor device is in an on state.
  • FIG. 6 is a schematic diagram of the transfer curve of the X-ray detector under the conditions of adding X-ray irradiation (corresponding to the upper curve) and without adding X-ray (corresponding to the lower curve).
  • the electron concentration in the channel semiconductor layer increases, and the output current increases.
  • a database is established for the corresponding currents obtained from different X-ray irradiation doses.
  • the thin-film transistor device can act as a photoelectric device.
  • the role of the sensor When a certain bias voltage is applied to the source electrode and the drain electrode of the thin film transistor, the output current of the transistor increases or decreases rapidly, which acts as an amplifier.
  • the preparation method of the all-inorganic transistor X-ray detector of this embodiment includes the following steps:
  • Step S1 a gate electrode is prepared on the substrate.
  • an evaporation coating method is used to grow a metal film on the surface of the substrate, or a highly impurity silicon substrate is used.
  • step S2 a gate insulating layer is prepared on the substrate and the gate electrode.
  • a gate insulating layer covering the substrate and the gate electrode is formed by processes such as spin coating, blade coating, vapor deposition, and thermal oxidation.
  • silicon dioxide with a thickness of 100 nm is formed on a highly doped n-type or p-type silicon wafer by thermal oxidation or chemical vapor deposition as a gate insulating layer.
  • step S3 a channel semiconductor layer is prepared on the gate insulating layer.
  • the channel semiconductor material is deposited on the upper surface of the gate insulating layer using a thin film deposition process.
  • magnetron sputtering is used to prepare indium gallium zinc oxide (IGZO) with a thickness of 40 nm on the gate dielectric material in step S2.
  • IGZO indium gallium zinc oxide
  • step S4 a source electrode and a drain electrode are prepared on the channel semiconductor layer.
  • an evaporation method is used to grow a metal thin film on the upper surface of the channel semiconductor layer, and a mask is used to pre-pattern the metal thin film to form a source electrode and a drain electrode.
  • step S3 aluminum oxide is thermally evaporated to a thickness of 100-200 nm.
  • the electrode width is 1000um, and the channel length is 100um.
  • Step S5 an X-ray absorption layer is prepared on the channel semiconductor layer.
  • X-ray absorbing materials in the form of quantum dots, nanowires or thin films are prepared on the channel semiconductor layer by spin coating, drop coating and other methods.
  • preparing the X-ray absorption layer on the channel semiconductor layer specifically includes:
  • Step S51 coating 5-10 ⁇ l of all-inorganic perovskite (cesium lead iodine bromide) with a concentration of 10 mg/ml on the surface of the IGZO-TFT channel;
  • step S52 after drying at room temperature to form a film, the sample in S51 is first immersed in the antisolvent of the inorganic perovskite quantum dots for 10s-180s to remove excess organic ligands in the organic perovskite quantum dots.
  • step S53 the sample in S52 is immersed in a solution of lead acetate or lead nitrate for 10s-180s.
  • solutions of lead acetate or lead nitrate use solvents that are antisolvents for inorganic perovskites.
  • step S6 a protective layer covering the entire upper surface of the device is prepared.
  • a thin film deposition process such as spin coating, blade coating, vapor deposition, sputtering, etc. is used to deposit an electrode protection layer on the upper surface of the upper absorption layer.
  • PMMA was spin-coated at a rotational speed of 2000 rpm, and the PMM concentration was 40 mg/ml.
  • the conductor material may be any one or more of gold, silver, copper, aluminum, molybdenum, nickel, indium tin oxide, indium zinc oxide, transparent conductive plastic, and conductive compound.
  • the material of the channel semiconductor layer is an organic or inorganic semiconductor material, such as indium gallium zinc oxide (IGZO), silicon.
  • the material of the X-ray absorbing layer is amorphous selenium, lead oxide, lead sulfide, mercury iodide, methylammonium lead iodide, antimony zinc cadmium (CZT), cesium lead iodine, cesium lead bromide or mixed cation/anion inorganic halogen perovskite Any one or more of mines.
  • the lower surface of the gate electrode 102 is connected to the substrate 101, the upper surface of the gate electrode 102 is connected to the lower surface of the gate insulating layer 103; the lower surfaces of the source electrode 106 and the drain electrode 107 are connected to the gate insulating layer 103 contacts, the channel semiconductor layer 104 covers the drain electrode 107, the source electrode 106 and the gate insulating layer 103; the channel semiconductor layer 104 is connected to the lower surface of the X-ray absorption layer, and the upper surface of the X-ray absorption layer is connected to the protective layer ;
  • the charge transport layer 108 is formed and covered on the channel semiconductor layer 104 ; the X-ray absorption layer is formed and covered on the charge transport layer 108 .
  • the difference between the device preparation of the fifth embodiment and the device preparation of the fourth embodiment is that: before preparing the channel layer, the drain electrode and the source electrode are prepared on the gate insulating layer by means of evaporation or sputtering; Or directly use the mask method to complete the patterning of the drain electrode and the source electrode.
  • the present invention adopts the heterojunction formed by the absorption layer of perovskite material (cesium lead iodine bromide) and the interface of the IGZO-TFT channel for X-ray detection, without the need for external bias to promote carrier injection into the channel , can work at lower voltage and save energy. Moreover, the covering and processing methods of the absorption layer of the perovskite material make the device structure simpler and facilitate the preparation.
  • perovskite material cesium lead iodine bromide

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Abstract

一种全无机晶体管型X射线探测器及其制备方法，该探测器包括衬底（101）、栅电极（102）、栅绝缘层（103）、沟道半导体层（104）、源电极（106）和漏电极（107）、X射线吸收层（105）和保护层，其中，在所述X射线吸收层（105）和所述沟道半导体层（104）建立异质结，在X射线照射下，该异质结使所产生的电子-空穴对分离，并使所述X射线吸收层（105）产生的载流子注入到所述沟道半导体层（104），从而无需设置顶电极，通过异质结界面将X射线吸收层（105）的非平衡载流子转移到沟道半导体层（104）中，可在低电压条件下工作，并且器件结构简单，易于制造。

Description

一种全无机晶体管型X射线探测器及其制备方法 技术领域
本发明涉及X射线探测器技术领域，尤其涉及一种全无机晶体管型X射线探测器及其制备方法。
背景技术
目前商用直接探测X射线平板探测器通常是基于非晶硒(a-Se)的平板探测器，非晶硒X射线平板探测器具有较宽的动态范围，能够满足低能X射线成像，如乳房X线照相术的要求(～20keV)。然而非晶硒平板X射线探测器为两端结构，不具有电荷增益功能，因而不具有信号放大功能，导致信噪比低。为了增强电荷信号，通常会将X射线直接探测器与场效应管集成使用，利用晶体管放大电信号。并且为了提高信号响应，通常需要在X射线吸收层上形成一层顶部电极，在顶部电极上施加偏压，使得X光照射产生的电子空穴分离，并将载流子注入到导电沟通中。
在现有技术中，如图1所示，典型的探测器结构均需设置顶电极，例如专利申请CN201811094472.2、CN201810563401.6CN201710977868.0等。由于这类探测器结构需要额外电极，不利于简化制备工艺。
发明内容
本发明的目的在于克服上述现有技术的缺陷，提供一种全无机晶体管型X射线探测器及其制备方法，通过采用恰当的异质结结构，促进光生载流子分离，可在低电压条件下工作。
根据本发明的第一方面，提供一种全无机晶体管型X射线探测器。该探测器包括衬底、栅电极、栅绝缘层、沟道半导体层、源电极和漏电极、X射线吸收层和保护层，其中，在所述X射线吸收层和所述沟道半导体层建立异质结，在X射线照射下，该异质结使所产生的电子-空穴对分离，并使所述X射线吸收层产生的载流子注入到所述沟道半导体层。
在一个实施例中，所述栅电极形成在所述衬底上；所述栅绝缘层形成在所述栅电极上；所述源电极和所述漏电极分别形成在所述栅绝缘层上；所述沟道半导体层形成在所述栅绝缘层、所述漏电极和所述源电极上；所 述X射线吸收层形成并覆盖在所述沟道半导体层上。
在一个实施例中，所述栅电极的下表面与所述衬底相连；所述栅电极的上表面与所述栅绝缘层的下表面相连；所述栅绝缘层的上表面与所述沟道半导体层的下表面相连；所述源电极下表面、所述漏电极下表面与所述沟道半导体层的上表面相连；所述源电极上表面、所述漏电极上表面分别与所述X射线吸收层下表面相连；所述X射线吸收层的上表面与所述保护层相连。
在一个实施例中，本发明提供的探测器还包括电荷传输层，其中，所述栅电极形成在所述衬底上；所述栅绝缘层形成在所述栅电极上；所述源电极和所述漏电极分别形成在所述栅绝缘层上；所述沟道半导体层形成在所述栅绝缘层、所述漏电极和所述源电极上；所述电荷传输层形成并覆盖在所述沟道半导体层上；所述X射线吸收层形成并覆盖在所述电荷传输层上。
在一个实施例中，所述栅电极的下表面与所述衬底相连，所述栅电极上表面与所述栅绝缘层的下表面相连；所述源电极下表面、所述漏电极下表面与所述栅绝缘层接触，所述沟道半导体层覆盖在所述漏电极、所述源 电极和所述栅绝缘层之上；所述沟道半导体层与所述X射线吸收层下表面相连；所述X射线吸收层的上表面与所述保护层相连。
在一个实施例中，所述X射线吸收层形成在所述衬底上；所述源电极和所述漏电极分别形成在所述X射线吸收层上；所述沟道半导体层形成并覆盖在所述X射线吸收层、所述漏电极和所述源电极上；所述栅绝缘层形成在所述沟道半导体上；所述栅电极形成在所述栅绝缘层上；所述保护层形成在所述栅电极上。
在一个实施例中，所述栅电极、所述漏电极和所述源电极由金、银、铜、铝、钼、镍、氧化铟锡、氧化铟锌、透明导电塑料、导电化合物、重掺杂半导体材料中的一种或多种制成。
在一个实施例中，所述沟道半导体层由非晶硅、单晶硅、多晶硅、氧化锡、氧化锌、铟镓氧化锌、二硫化钼、碘化铅等半导体材料的一种或者多种制成。
在一个实施例中，所述X射线吸收层包含非晶硒、氧化铅，硫化铅、碘化汞、甲氨碘化铅、锑锌镉、铯铅碘、铯铅溴或混合阳离子/阴离子无机卤素钙钛矿的一种或多种。
根据本发明的第二方面，提供一种全无机晶体管型X射线探测器的制备方法，包括：在衬底上制备栅电极；在所述衬底和所述栅电极上制备栅绝缘层；在所述栅绝缘层上制备沟道半导体层；在所述沟道半导体层上制备源电极和漏电极；在所述沟道半导体层上制备X射线吸收层；制备覆盖整个探测器上表面的保护层。
与现有技术相比，本发明的优点在于，无需设置顶电极，通过异质结界面将吸收层的非平衡载流子转移到晶体管沟道中，可在低电压条件下工作。本发明器件结构简单，易于制造，并且使用过程能够节省能量。
附图说明
以下附图仅对本发明作示意性的说明和解释，并不用于限定本发明的范围，其中：
图1是现有技术的典型探测器的结构示意图；
图2是根据本发明一个实施例的底栅底接触无电荷传输层的X射线探测器示意图；
图3是根据本发明一个实施例的底栅底接触有电荷传输层的X射线探 测器示意图；
图4是根据本发明一个实施例的顶栅顶接触无电荷传输层的X射线探测器示意图；
图5是光电子注入型X射线探测器的等效电路图；
图6是根据本发明一个实施例的加X射线照射和不加X射线条件下，X射线探测器的转移曲线示意图。
具体实施方式
为了使本发明的目的、技术方案、设计方法及优点更加清楚明了，以下结合附图通过具体实施例对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明。
在本文示出和讨论的所有例子中，任何具体值应被解释为仅仅是示例性的，而不是作为限制。因此，示例性实施例的其它例子可以具有不同的值。
对于相关领域普通技术人员已知的技术、方法和设备可能不作详细讨论，但在适当情况下，所述技术、方法和设备应当被视为说明书的一部分。
本发明提供的全无机晶体管型X射线探测器的原理是：利用X射线吸收层与沟道层(或称沟道半导体层)之间形成的异质结，直接将X光照射产生的电子/空穴注入沟道层。由于载流子的注入，会使漏电极和源电极之间的电流显著增加或使TFT(薄膜晶体管)的阈值电压偏移，从而实现对X射线的探测。
以下将具体介绍本发明提供的全无机晶体管型X射线探测器类型和对应的制备方法。
实施例一
参见图2，其是底栅底接触无电荷传输层的示例，该X射线探测器具体包括：衬底101；栅电极102，形成在衬底101上；栅绝缘层(或称介电层)103，形成在栅电极102上；源电极106和漏电极107，分别形成在栅绝缘层103上；沟道半导体层104，形成在栅绝缘层103、漏电极107、和源电极106上；X射线吸收层105，形成并覆盖在沟道半导体层104上。
实施例二
参见图3，其是底栅底接触有电荷传输层的示例，该X射线探测器具体包括：衬底101；栅电极102，形成在衬底101上；栅绝缘层103，形成 在栅电极102上；源电极106和漏电极107，分别形成在栅绝缘层103上；沟道半导体层104，形成在栅绝缘层103、漏电极107和源电极106上；电荷传输层108，形成并覆盖在沟道半导体层104上；X射线吸收层105，形成并覆盖在电荷传输层108上。
实施例三
参见图4，其是顶栅顶接触无电荷传输层的示例，该X射线探测器具体包括：衬底101；X射线吸收层105，形成在衬底101上；源电极106和漏电极107，分别形成在X射线吸收层105上；沟道半导体层104，形成并覆盖在X射线吸收层105、漏电极107和源电极106上；栅绝缘层103，形成在沟道半导体层104上；栅电极102，形成在栅绝缘层103上；保护层(未示出)，形成在栅电极102上；
在上述实施例中，所提供的晶体管型X射线探测器基于的原理是：X射线吸收层产生非平衡载流子，在吸收层、电荷传输层和沟道半导体层所形成异质结的作用下，使得器件受X射线照射时所产生的电子-空穴对迅速分离，并且使载流子注入沟道层中，使得沟道层中的载流子浓度增大，有效增大光电流，提高X射线探测器件的光电特性，从而提高光电子注入 型X射线探测器件的灵敏度。特别是，在采用高迁移率的半导体材料制备沟道半导体层情况下，探测器的响应速度得到有效增大。
优选地，栅电极102、漏电极107和源电极106由金、银、铜、铝、钼、镍、氧化铟锡、氧化铟锌、透明导电塑料、导电化合物、重掺杂半导体材料中的任意一种或多种制成。
优选地，沟道半导体层104由非晶硅、单晶硅、多晶硅、氧化锡、氧化锌、铟镓氧化锌、二硫化钼、碘化铅等半导体材料的一种或者几种制成。
优选地，X射线吸收层105的材料为包含非晶硒、氧化铅，硫化铅、碘化汞、甲氨碘化铅、锑锌镉(CZT)、铯铅碘、铯铅溴或混合阳离子/阴离子无机卤素钙钛矿的任意一种或多种。
需说明的是，以上实施例仅作为典型器件结构参考，任何形式的调换功能层顺序所产生的变形方案均在本发明的保护范围之内。
根据本发明的第二方面，提供一种全无机晶体管型X射线探测器，即基于异质结的光电子注入型X射线直接探测器的制备方法，以图2的晶体管型X射线探测器为例，其通过吸收层和沟道层建立起的异质结，形成内建电场，该电场使得X射线作用于吸收层产生的电子空穴对迅速分离，使 得载流子被内建电场注入到沟道半导体层中。当器件工作在开态时，能够有效增大光电流，提高晶体管型X射线探测器件的光电特性，从而增强X射线的灵敏度。此外，由于沟道半导体层所选用的材料具有较大的迁移率，使得本发明具有较快的响应速度。而且这种结构同时具有开关、放大器、传感器和电容的功能。
实施例四
结合图2，在该实施例中，栅电极102的下表面与衬底101相连，栅电极102的上表面与栅绝缘层103的下表面相连；栅绝缘层103的上表面与沟道半导体层104的下表面相连；源电极106的下表面、漏电极107的下表面与沟道半导体层104的上表面相连；源电极106的上表面、漏电极107的上表面分别与X射线吸收层105下表面相连，X射线吸收层105的上表面与保护层(未示出)相连。
在该实施例中，栅绝缘层103覆盖栅电极102和衬底101，衬底101可选用单晶硅片，玻璃或者塑料材质等。
优选地，沟道半导体层104的材料为单晶硅，多晶硅，铟镓氧化锌，氧化锌，氧化锡，卤素钙钛矿薄膜材料等的一种或者几种。
优选地，X射线吸收层105的材料为包含非晶硒、氧化铅，碘化汞，甲氨碘化铅、锑锌镉(CZT)或钙钛矿等X射线探测材料的任意一种或多种。X射线吸收层的载流子浓度随着X射线剂量的变化而变化。
优选地，栅电极102选用铝、钼、铬、钛、镍、金属以及氧化铟锡、氧化铟锌、透明导电塑料或导电玻璃中的任意一种或多种材料制备。
优选地，源电极106和漏电极107选用铝、钼、铬、钛、镍等材料中的任意一种或多种制备。栅电极102、源电极106和漏电极107均选用高电导率材料制备。
图5是光电子注入型X射线探测器的等效电路图，其中，D表示漏电极，G表示栅电极，S表示源电极。可见，本发明可等效为X射线光吸收层-沟道层之间形成的二极管与薄膜晶体管的集成器件。当X射线照射时，会使得吸收层中载流子浓度增大，电子会在异质结内建电场的作用下被注入到薄膜晶体管的导电沟道中，改变薄膜晶体管的电流大小，起到X射线传感器使用。当栅电极和源电极加上合适栅偏压，且薄膜晶体管器件的输出电流小于一定值时，本发明的探测器件处于关闭状态；当输出电流大于或等于一定值时，本发明的探测器件处于开启状态，可起到开关的作用。 例如，在实际电路中，可设定当该薄膜晶体管器件输出电流小于1nA时,该薄膜晶体管器件处于关闭状态，当薄膜晶体管器件输出电流大于或等于1nA时，该薄膜晶体管器件处于开启状态。
图6是加X射线照射(对应上方曲线)和不加X射线(对应下方曲线)条件下，X射线探测器的转移曲线示意，当X射线照射本发明实施例的薄膜晶体管器件时，其沟道半导体层中电子浓度增大，输出电流增大。对不同X射线照射剂量得到的对应电流建立数据库，通过读出薄膜晶体管器件暴露在X射线下的电流强度，就可计算得到该环境下的X射线剂量，此时的薄膜晶体管器件便起到光电传感器的作用。当薄膜晶体管的源电极，漏电极施加一定偏压时，使得晶体管的输出电流迅速增大或减小，起到放大器的作用。
仍结合图2，该实施例的全无机晶体管型X射线探测器的制备方法包括以下步骤：
步骤S1，在衬底上制备栅电极。
例如，采用蒸发镀膜法在衬底的表面生长一层金属薄膜，或采用高参杂的硅片衬底。
步骤S2，在衬底和栅电极上制备栅绝缘层。
例如，利用旋涂，刮涂，气相沉积，热氧化等工艺，形成覆盖衬底和栅电极的栅绝缘层。
具体地，在高掺杂n型或p型硅片上热氧化或采用化学气相沉积形成100nm厚的二氧化硅，作为栅绝缘层。
步骤S3，在栅绝缘层上制备沟道半导体层。
例如，采用薄膜沉积工艺在栅绝缘层的上表面沉积沟道半导体材料。
具体地，在步骤S2中的栅介电材料上采用磁控溅射制备40nm厚的氧化铟镓锌(IGZO)。
步骤S4，在沟道半导体层上制备源电极和漏电极。
例如，采用蒸镀法在沟道半导体层的上表面生长一层金属薄膜，利用掩膜版将所述金属薄膜预定图形，形成源电极和漏电极。
具体地，在步骤S3中的沟道半导体层上，热蒸镀氧铝，厚度100-200nm。电极宽1000um，沟道长度为100um。
步骤S5，在沟道半导体层上制备X射线吸收层。
例如，利用旋涂、滴涂等方法在沟道半导体层上制备量子点、纳米线 或者薄膜形态的X射线吸收材料。
在一个实例中，在沟道半导体层上制备X射线吸收层具体包括：
步骤S51，将5-10μl，浓度为10mg/ml的全无机钙钛矿(铯铅碘溴)涂敷于IGZO-TFT沟道表面；
步骤S52，待室温下干燥成膜后，将S51中的样品先浸入无机钙钛矿量子点的抗溶剂中，保持10s-180s，除去机钙钛矿量子点中多余的有机配体。
步骤S53，将S52中的样品浸入醋酸铅或硝酸铅的溶液中，保持10s-180s。
例如，醋酸铅或硝酸铅的溶液所用溶剂为无机钙钛矿的抗溶剂。
步骤S6，制备覆盖整个器件上表面的保护层。
例如，利用旋涂、刮涂、蒸镀、溅射等薄膜沉积工艺，在上吸收层的上表面沉积形成覆盖衬上电极保护层。
具体地，在X射线吸收层上，旋涂PMMA，转速2000rpm，PMM浓度40mg/ml。
在本发明实施例中，导体材料可以是金、银、铜、铝、钼、镍、氧化 铟锡、氧化铟锌、透明导电塑料、导电化合物中的任意一种或多种。沟道半导体层的材料为有机或无机半导体材料，例如氧化铟镓锌(IGZO)，硅。X射线吸收层的材料为非晶硒、氧化铅，硫化铅、碘化汞、甲氨碘化铅、锑锌镉(CZT)、铯铅碘、铯铅溴或混合阳离子/阴离子无机卤素钙钛矿的任意一种或多种。
实施例五
其他类型的全无机晶体管型X射线探测器的制备方法可参考上述实施例四，在此不再赘述。例如，对于图3的示例，栅电极102的下表面与衬底101相连，栅电极102的上表面与栅绝缘层103的下表面相连；源电极106、漏电极107的下表面与栅绝缘层103接触，沟道半导体层104覆盖在漏电极107、源电极106和栅绝缘层103之上；沟道半导体层104与X射线吸收层下表面相连，X射线吸收层的上表面与保护层相连；电荷传输层108形成并覆盖在沟道半导体层104上；X射线吸收层形成并覆盖在电荷传输层108上。
该实施例五的器件制备与实施例四的器件制备不同之处在于：在制备沟道层之前，利用蒸镀或溅射的方法，在栅绝缘层上制备漏电极和源电极； 利用光刻或直接采用掩膜版的方法，完成漏电极和源电极的图形化。
综上所述，本发明采用钙钛矿材料(铯铅碘溴)吸收层和IGZO-TFT沟道界面形成的异质结，用于X射线探测，无需外加偏压促进载流子注入沟道，能在较低电压下工作，节省能量。并且，对于钙钛矿材料吸收层的覆盖和处理方式，使器件结构更加简单，便于制备。
需要说明的是，虽然上文按照特定顺序描述了各个步骤，但是并不意味着必须按照上述特定顺序来执行各个步骤，实际上，这些步骤中的一些可以并发执行，甚至改变顺序，只要能够实现所需要的功能即可。
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。本文中所用术语的选择，旨在最好地解释各实施例的原理、实际应用或对市场中的技术改进，或者使本技术领域的其它普通技术人员能理解本文披露的各实施例。

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  1. 一种全无机晶体管型X射线探测器，包括衬底、栅电极、栅绝缘层、沟道半导体层、源电极和漏电极、X射线吸收层和保护层，其中，在所述X射线吸收层和所述沟道半导体层建立异质结，在X射线照射下，该异质结使所产生的电子-空穴对分离，并使所述X射线吸收层产生的载流子注入到所述沟道半导体层。
  2. 根据权利要求1所述的全无机晶体管型X射线探测器，其中，所述栅电极形成在所述衬底上；所述栅绝缘层形成在所述栅电极上；所述源电极和所述漏电极分别形成在所述栅绝缘层上；所述沟道半导体层形成在所述栅绝缘层、所述漏电极和所述源电极上；所述X射线吸收层形成并覆盖在所述沟道半导体层上。
  3. 根据权利要求2所述的全无机晶体管型X射线探测器，其中，所述栅电极的下表面与所述衬底相连；所述栅电极的上表面与所述栅绝缘层的下表面相连；所述栅绝缘层的上表面与所述沟道半导体层的下表面相连；所述源电极下表面、所述漏电极下表面与所述沟道半导体层的上表面相连；所述源电极上表面、所述漏电极上表面分别与所述X射线吸收层下 表面相连；所述X射线吸收层的上表面与所述保护层相连。
  4. 根据权利要求1所述的全无机晶体管型X射线探测器，还包括电荷传输层，其中，所述栅电极形成在所述衬底上；所述栅绝缘层形成在所述栅电极上；所述源电极和所述漏电极分别形成在所述栅绝缘层上；所述沟道半导体层形成在所述栅绝缘层、所述漏电极和所述源电极上；所述电荷传输层形成并覆盖在所述沟道半导体层上；所述X射线吸收层形成并覆盖在所述电荷传输层上。
  5. 根据权利要求4所述的全无机晶体管型X射线探测器，其中，所述栅电极的下表面与所述衬底相连，所述栅电极上表面与所述栅绝缘层的下表面相连；所述源电极下表面、所述漏电极下表面与所述栅绝缘层接触，所述沟道半导体层覆盖在所述漏电极、所述源电极和所述栅绝缘层之上；所述沟道半导体层与所述X射线吸收层下表面相连；所述X射线吸收层的上表面与所述保护层相连。
  6. 根据权利要求1所述的全无机晶体管型X射线探测器法，其中，所述X射线吸收层形成在所述衬底上；所述源电极和所述漏电极分别形成在所述X射线吸收层上；所述沟道半导体层形成并覆盖在所述X射线吸 收层、所述漏电极和所述源电极上；所述栅绝缘层形成在所述沟道半导体上；所述栅电极形成在所述栅绝缘层上；所述保护层形成在所述栅电极上。
  7. 根据权利要求1所述的全无机晶体管型X射线探测器，其中，所述栅电极、所述漏电极和所述源电极由金、银、铜、铝、钼、镍、氧化铟锡、氧化铟锌、透明导电塑料、导电化合物、重掺杂半导体材料中的一种或多种制成。
  8. 根据权利要求1所述的全无机晶体管型X射线探测器，其中，所述沟道半导体层由非晶硅、单晶硅、多晶硅、氧化锡、氧化锌、铟镓氧化锌、二硫化钼、碘化铅等半导体材料的一种或者多种制成。
  9. 根据权利要求1所述的全无机晶体管型X射线探测器，其中，所述X射线吸收层包含非晶硒、氧化铅，硫化铅、碘化汞、甲氨碘化铅、锑锌镉、铯铅碘、铯铅溴或混合阳离子/阴离子无机卤素钙钛矿的一种或多种。
  10. 一种全无机晶体管型X射线探测器的制备方法，包括：
    在衬底上制备栅电极；
    在所述衬底和所述栅电极上制备栅绝缘层；
    在所述栅绝缘层上制备沟道半导体层；
    在所述沟道半导体层上制备源电极和漏电极；
    在所述沟道半导体层上制备X射线吸收层；
    制备覆盖整个探测器上表面的保护层。
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