阅读说明：本技术 一种基于钙钛矿雪崩管的高灵敏度探测结构及制备方法 (Perovskite avalanche transistor-based high-sensitivity detection structure and preparation method thereof ) 是由 雷威 周建明 朱莹 于 2021-10-18 设计创作，主要内容包括：本发明提供一种基于钙钛矿雪崩管的高灵敏度探测结构及制备方法,涉及高灵敏度X射线/γ射线探测领域,本发明包括以下部分：采用厚度大于1厘米的本征钙钛矿晶体作为X射线/γ射线光子吸收体,利用钙钛矿晶体的高吸收系数,获得较高的X射线/γ射线光子吸收转换效率,利用本征钙钛矿晶体的高电阻率,减小探测器暗电流,在本征晶体上顺序生长空间电荷层、宽带隙钙钛矿倍增层和窄带隙钙钛矿倍增层,对光生电子空穴对雪崩倍增,获得高增益探测信号,与常规采用闪烁体的间接雪崩探测器件相比较,它避免了将X射线/γ射线光子转换为可见光子的过程,因此可以具有更高的探测量子效率。(The invention provides a perovskite avalanche transistor-based high-sensitivity detection structure and a preparation method thereof, relating to the field of high-sensitivity X-ray/gamma-ray detection and comprising the following parts: the intrinsic perovskite crystal with the thickness of more than 1 cm is used as an X-ray/gamma-ray photon absorber, the high absorption coefficient of the perovskite crystal is utilized to obtain higher X-ray/gamma-ray photon absorption conversion efficiency, the high resistivity of the intrinsic perovskite crystal is utilized to reduce the dark current of a detector, a space charge layer, a wide-band gap perovskite multiplication layer and a narrow-band gap perovskite multiplication layer are sequentially grown on the intrinsic crystal to multiply the avalanche of photoelectron-induced holes to obtain a high-gain detection signal, and compared with a conventional indirect avalanche detection device adopting a scintillator, the high-gain detection device avoids the process of converting X-ray/gamma-ray photons into visible photons, so that the high-gain detection quantum efficiency can be higher.)

1. A high sensitivity detects structure based on perovskite avalanche pipe which characterized in that: the device comprises an intrinsic perovskite crystal, a p-type epitaxial layer, a space charge layer, a wide band gap perovskite multiplication layer and a narrow band gap perovskite multiplication layer;

the intrinsic perovskite crystal is an absorption and conversion layer of X-ray/gamma-ray photons;

the lower end of the perovskite intrinsic absorption layer is provided with a p-type perovskite crystal epitaxial layer, the lower end of the p-type perovskite crystal epitaxial layer is provided with an incident end electrode, and an exhausted built-in electric field is formed at the interface between the p-type perovskite crystal epitaxial layer and the perovskite intrinsic absorption layer and is used for blocking the injection of external carriers and inhibiting dark current;

the upper end of the perovskite intrinsic absorption layer is provided with a heavily doped n-type perovskite crystal epitaxial layer serving as a space charge layer of the avalanche transistor, and a depletion layer is formed on an interface between the perovskite intrinsic absorption layer and the space charge layer and is used for forming a large voltage drop between the perovskite intrinsic absorption layer and the space charge layer;

the high-resistance wide-band gap perovskite multiplication layer is arranged on the space charge layer, the voltage drop of the high-resistance wide-band gap perovskite multiplication layer is larger than the avalanche breakdown threshold voltage of the high-resistance wide-band gap perovskite multiplication layer, and the detection current gain is improved through impact ionization;

a narrow-band-gap perovskite multiplication layer is arranged on the wide-band-gap perovskite multiplication layer, the narrow-band-gap perovskite multiplication layer is used for increasing the multiplication carrier concentration, and the detection current gain is further improved;

and an exit end electrode is arranged at the upper end of the narrow-band-gap perovskite multiplication layer, the entrance end electrode is grounded, and positive voltage is applied to the exit end electrode to form a reverse bias absorption, space charge and multiplication separation avalanche diode.

2. The perovskite avalanche transistor-based high-sensitivity detection structure according to claim 1, wherein: the thickness of the perovskite intrinsic absorption layer is generally several millimeters to one centimeter, and the perovskite intrinsic absorption layer has high resistivity and large carrier mobility;

the perovskite intrinsic absorber layer maintains more than 10⁵The electric field strength of V/m is used for effectively separating photon-generated carriers and reducing noise current.

3. The preparation method of the perovskite avalanche transistor-based high-sensitivity detection structure according to claim 1, characterized by comprising the following preparation steps:

1) preparing an intrinsic perovskite crystal with the thickness of more than 1 cm by adopting a solution inverse temperature crystallization method;

2) growing epitaxial layers on the upper end and the lower end of the intrinsic perovskite crystal by adopting a solution epitaxy method, and adding proper metal ions into the precursor solution to enable the epitaxial layers to respectively present a p type and an n type;

3) exposing crystal faces of the p-type epitaxial layer and the n-type epitaxial layer by a crystal cutting method, and depositing an incident end metal electrode on the p-type epitaxial layer by a vacuum evaporation method;

4) growing another epitaxial layer on the n-type epitaxial layer by a solution epitaxy method, and regulating and controlling the concentration of doped metal salt in the precursor solution to obtain the heavy doping characteristic;

5) respectively growing a high-resistance wide-band gap perovskite multiplication layer and a narrow-band gap perovskite multiplication layer on the heavily-doped n-type epitaxial layer by adopting a solution epitaxial method;

6) and preparing an emergent surface electrode on the narrow-band-gap perovskite multiplication layer by adopting a vacuum evaporation method.

Technical Field

The invention relates to the field of high-sensitivity X-ray/gamma-ray detection, in particular to a perovskite avalanche transistor-based high-sensitivity detection structure and a preparation method thereof.

Background

X-ray/gamma-ray detection has important applications in the fields of nuclear medicine, aerospace, industrial nondestructive testing and the like, and people are constantly working on developing high-performance X-ray/gamma-ray detectors. Since the x-ray/gamma-ray photon has high energy and strong penetration ability, the x-ray/gamma-ray detection active material needs to have a high average atomic number (Z) and thickness to sufficiently absorb the x-ray/gamma-ray photon. High-purity semiconductor single crystals are generally selected as active materials for direct detection of x-ray/gamma-ray photons, and in the 70 s, gamma-ray detection using high-purity ge (hpge) was proposed to achieve good energy resolution. But requires liquid nitrogen cooling due to its small band gap. In order to detect x-rays/gamma-rays at room temperature, compound semiconductor crystals, such as CdTe, Cd1-xznxte (czt), and TlBr, etc., have been used as active materials for gamma-ray detection, and these x-ray/gamma-ray detectors have been commercially used. However, the existing compound semiconductor x-ray/gamma-ray detector has the problems of complex preparation technology, high cost, incompatibility of a sensing unit and a reading circuit process and the like.

In medical imaging, in particular Single Photon Emission Computed Tomography (SPECT) and Positron Emission Tomography (PET) techniques, the photon flux of x-rays or gamma-rays is low and must be detected in the form of photon counts. Since the incident x-ray/gamma ray is very weak, it is necessary to provide a very large gain to the photo-generated current in photon counting detection, and it is also necessary to suppress dark current and noise as much as possible to avoid the annihilation of the weak detection signal by the noise.

Avalanche diodes (APDs) are a detector structure often employed for photon counting in order to obtain high gain of the photo-generated current signal. Avalanche diodes can achieve very high gain (greater than 100) through impact ionization of carriers, but impact ionization requires application of very high bias voltage, and impact ionization is random, so that dark current and noise of the avalanche diode are usually high, which is not favorable for photon counting detection. In order to solve this problem, avalanche diodes (SAM APDs) have been proposed in which a photon absorption region and a multiplication region are separated, as shown in fig. 1, and in order to further reduce the multiplication threshold voltage and noise, a structure of an SACM APD has been proposed in which a photon absorption region, a space charge region, and a multiplication region are separated, as shown in fig. 2.

The SAM APD and the SACM APD both adopt a multi-element inorganic compound semiconductor as an active material, an epitaxial layer grows by methods such as molecular beam epitaxy, organic metal chemical vapor deposition and the like, doping is carried out by means of ion implantation and the like, and the thickness of the crystal and the epitaxial layer is generally within 10 micrometers. If the incident light is x-ray/gamma ray, the photon energy is very high, and the existing SAM APD and SACM APD have very weak absorption and conversion to x-ray/gamma ray photon, so people generally amplify the x-ray/gamma ray photon avalanche by an indirect detection mode, and a typical structure is shown in fig. 3 (CN 106415319A, WO2016/060102, JA 2016.04.21), in which, x-ray/gamma ray photon firstly enters a scintillator, and they react with the scintillator to generate visible fluorescence emission, and then the scintillation fluorescence is detected by the compound semiconductor avalanche diode, in which, the x-ray/gamma ray photon is firstly converted into visible photon, and then the visible photon is converted into electric signal. Thus, this indirect detection method reduces the external quantum efficiency of x-ray/gamma-ray photon detection and introduces additional noise.

Aiming at the problems of the indirect avalanche detection of the x-ray/gamma-ray, a structure and a preparation method of a high-efficiency direct avalanche detection device of the x-ray/gamma-ray are needed to be found, although people can carry out direct detection of the x-ray/gamma-ray by adopting materials such as CdZnTe and the like, the preparation cost of the detection devices is high, and the effective detection area is greatly limited.

The perovskite material has excellent photoelectric property, and has good application prospect in the fields of photovoltaic solar cells, UV/Vis/NIR photoelectric detection, light-emitting diodes and the like. The perovskite single crystal has the advantages of wide band gap (-3.1 eV), containing heavy elements such as lead and halogen, having the carrier mobility as high as more than 600cm < 2 > -2V-1S < -1 >, the carrier service life as long as several microseconds, the ionization energy as high as 3-5 eV, being very cheap to prepare by using a solution method and the like, and in addition, compared with other semiconductors, the halogen perovskite also has very good anti-irradiation property.

The invention provides a device structure for direct avalanche detection of X-ray/gamma ray and a preparation method thereof by utilizing the structural characteristics of perovskite materials and the advantages of a solution method preparation process, the preparation cost is low, and the X-ray/gamma ray detection with high sensitivity, high gain, low threshold voltage and low noise can be obtained.

Disclosure of Invention

The invention aims to provide a perovskite avalanche transistor-based high-sensitivity detection structure and a preparation method thereof, so as to solve the technical problems.

In order to solve the technical problems, the invention adopts the following technical scheme:

a high-sensitivity detection structure based on a perovskite avalanche transistor comprises an intrinsic perovskite crystal, a p-type epitaxial layer, a space charge layer, a wide-bandgap perovskite multiplication layer and a narrow-bandgap perovskite multiplication layer;

the intrinsic perovskite crystal is an absorption and conversion layer of X-ray/gamma-ray photons;

the lower end of the perovskite intrinsic absorption layer is provided with a p-type perovskite crystal epitaxial layer, the lower end of the p-type perovskite crystal epitaxial layer is provided with an incident end electrode, and an exhausted built-in electric field is formed at the interface between the p-type perovskite crystal epitaxial layer and the perovskite intrinsic absorption layer and is used for blocking the injection of external carriers and inhibiting dark current;

the upper end of the perovskite intrinsic absorption layer is provided with a heavily doped n-type perovskite crystal epitaxial layer serving as a space charge layer of the avalanche transistor, and a depletion layer is formed on an interface between the perovskite intrinsic absorption layer and the space charge layer and is used for forming a large voltage drop between the perovskite intrinsic absorption layer and the space charge layer;

the high-resistance wide-band gap perovskite multiplication layer is arranged on the space charge layer, the voltage drop of the high-resistance wide-band gap perovskite multiplication layer is larger than the avalanche breakdown threshold voltage of the high-resistance wide-band gap perovskite multiplication layer, and the detection current gain is improved through impact ionization;

a narrow-band-gap perovskite multiplication layer is arranged on the wide-band-gap perovskite multiplication layer, the narrow-band-gap perovskite multiplication layer is used for increasing the multiplication carrier concentration, and the detection current gain is further improved;

and an exit end electrode is arranged at the upper end of the narrow-band-gap perovskite multiplication layer, the entrance end electrode is grounded, and positive voltage is applied to the exit end electrode to form a reverse bias absorption, space charge and multiplication separation avalanche diode.

Preferably, the thickness of the perovskite intrinsic absorption layer is generally several millimeters to one centimeter, and the perovskite intrinsic absorption layer has high resistivity and large carrier mobility; the perovskite intrinsic absorber layer maintains more than 10⁵The electric field strength of V/m is used for effectively separating photon-generated carriers and reducing noise current.

A preparation method of a high-sensitivity detection structure based on a perovskite avalanche transistor is characterized by comprising the following preparation steps:

1) preparing an intrinsic perovskite crystal with the thickness of more than 1 cm by adopting a solution inverse temperature crystallization method;

2) growing epitaxial layers on the upper end and the lower end of the intrinsic perovskite crystal by adopting a solution epitaxy method, and adding proper metal ions into the precursor solution to enable the epitaxial layers to respectively present a p type and an n type;

3) exposing crystal faces of the p-type epitaxial layer and the n-type epitaxial layer by a crystal cutting method, and depositing an incident end metal electrode on the p-type epitaxial layer by a vacuum evaporation method;

4) growing another epitaxial layer on the n-type epitaxial layer by a solution epitaxy method, and regulating and controlling the concentration of doped metal salt in the precursor solution to obtain the heavy doping characteristic;

5) respectively growing a high-resistance wide-band gap perovskite multiplication layer and a narrow-band gap perovskite multiplication layer on the heavily-doped n-type epitaxial layer by adopting a solution epitaxial method;

6) and preparing an emergent surface electrode on the narrow-band-gap perovskite multiplication layer by adopting a vacuum evaporation method.

The invention has the beneficial effects that:

1. the invention designs and prepares an X-ray/gamma-ray avalanche detection device by utilizing perovskite crystal, directly converts incident X-ray/gamma-ray photons into electron-hole pairs, multiplies the avalanche of the photon-generated electron-hole pairs to obtain a high-gain detection signal, and compared with the conventional indirect avalanche detection device adopting a scintillator, the device avoids the process of converting the X-ray/gamma-ray photons into visible photons, thereby having higher quantum detection efficiency.

2. In the technical scheme provided by the invention, the SACM APD structure is adopted to carry out X-ray/gamma-ray detection, and the method has the advantages of high sensitivity, high gain, low threshold voltage and low noise.

3. In the technical scheme provided by the invention, the perovskite intrinsic crystal substrate is prepared by adopting an inverse temperature method, and the p-type epitaxial layer and the n-type epitaxial layer are prepared by adopting a solution epitaxial doping method, so that the preparation method is relatively simple and the cost is low.

Drawings

FIG. 1 is a SAM APD structure;

FIG. 2 is a SACM APD structure;

FIG. 3 is an x-ray/gamma-ray indirect avalanche detection configuration;

FIG. 4 shows the structure and typical electric field distribution of a high-sensitivity X-ray/gamma-ray detector based on a perovskite avalanche transistor according to the present invention;

FIG. 5 is a typical X-ray/gamma-ray avalanche detection photocurrent-voltage curve;

FIG. 6 is a schematic view of the process of growing perovskite crystal by inverse temperature method and epitaxial doping by solution method.

The notation in the figure is: 1. incident x-rays/gamma-rays; 2. an incident end electrode; 3. a p-type perovskite epitaxial layer; 4. an ultra-thick intrinsic perovskite photon absorption layer; 5. an n-type perovskite barrier layer and an n + type space charge layer; 6. a high-resistance wide-band-gap perovskite multiplication layer; 7. a narrow band gap perovskite multiplication layer; 8. an exit terminal electrode; 9. a reverse bias voltage; 10. electric field distribution of the p-type barrier layer; 11. electric field distribution of the x-ray/gamma-ray photon absorption layer; 12. electric field distribution of the space charge layer; 13. wide band gap multiplication region electric field distribution; 14. narrow bandgap multiplication region electric field distribution; 15. n-type substrate Al_xGa_1-xN (x is more than or equal to 0 and less than or equal to 0.15); 16. an n-type metal electrode; 17. an intrinsic GaN photon absorption layer; 18. an n-type GaN barrier layer; 19. an intrinsic GaN avalanche layer; 20. a p-type GaN contact layer; 21. a p-type metal electrode; 22. a GaSb substrate; 23. n type Al_0.7An InAsSb contact layer; 24. an incident Ti/Au electrode; 25. pure Al_0.7An InAsSb multiplication layer; 26. p type Al_0.7An InAsSb space charge layer; 27. p type Al_0.3–0.7An InAsSb transition layer; 28. pure Al_0.3An InAsSb photon absorption layer; 29. p type Al_0.3An InAsSb barrier layer; 30. p type Al_0.7An InAsSb barrier layer; 31. heavily doped p-type Al_0.7An InAsSb contact layer; 32. emitting the Ti/Au electrode; 33. a probe housing; 34. an optical contact layer; 35. processing the circuit layer; 36. APD photoelectric conversion; 37. a scintillator; 38. a heating stage; 39. a growth dish; 40. a precursor solution; 41. growing by a reverse temperature method; 42. perovskite crystals; 43. an intrinsic perovskite substrate; 44. epitaxial doping by a solution method; 45. adding metal ions into the precursor solution; 46. growing an epitaxial layer and doping; 47. crystal cutting along the cutting line; 48. cutting the intrinsic perovskite substrate; 49. the epitaxial layer is doped.

Detailed Description

In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easily understood, the invention is further described below with reference to the specific embodiments and the attached drawings, but the following embodiments are only the preferred embodiments of the invention, and not all embodiments. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention.

The intrinsic perovskite crystal with the thickness of more than 1 cm is used as an X-ray/gamma-ray photon absorber, the high absorption coefficient of the perovskite crystal is utilized to obtain higher X-ray/gamma-ray photon absorption conversion efficiency, and the high resistivity of the intrinsic perovskite crystal is utilized to reduce the dark current of the detector.

A p-type layer and an n-type layer are arranged at two ends of the intrinsic perovskite crystal photon absorption layer to form a perovskite p-i-n junction, and under the reverse bias voltage 9, the depletion layer of the perovskite p-i-n junction is used for blocking external carrier injection, so that the detection dark current and noise are further reduced.

A space charge layer is arranged on the n-type perovskite epitaxial layer, and the doping concentration of the space charge layer and the thickness of the space charge layer are optimized, so that a depletion layer is expanded to the whole space charge layer, and the voltage drop of the space charge layer is improved.

The high-resistance wide-band-gap perovskite multiplication layer 6 is arranged on the space charge layer and used as an avalanche multiplication region of a photon-generated carrier, and the potential distribution of the space charge layer is regulated and controlled, so that the threshold electric field intensity required by avalanche can be achieved by applying smaller voltage to the multiplication region, the electric field intensity of the multiplication region is uniform as much as possible, and the avalanche breakdown voltage and noise are reduced.

The narrow-band-gap perovskite multiplication layer 7 is arranged on the high-resistance wide-band-gap perovskite multiplication layer 6, and the carrier concentration is improved by utilizing the narrow-band-gap perovskite multiplication layer 7, so that the gain of avalanche multiplication is increased.

In the avalanche multiplication detection structure, it is necessary to ensure that each epitaxial layer has better lattice matching and thermal expansion matching to reduce the defect density near the interface, and in order to achieve this, an excessive buffer layer may be provided between the epitaxial layers.

In specific practice, intrinsic perovskite crystals 4, such as MAPbBr, are first grown 41 to a thickness of greater than 1 cm by reverse temperature growth_2.5Cl_0.5The intrinsic perovskite layer is used as an x-ray/gamma-ray photon absorption layer, and a p-type perovskite epitaxial layer 3, such as Ag, is prepared on the lower end surface of an intrinsic perovskite crystal 4 by a solution epitaxial doping method⁺Doping with MAPBBr₃(ii) a An n-type perovskite epitaxial layer 5 is prepared by solution epitaxial doping of the upper end face of an intrinsic perovskite crystal 4, e.g. Bi³⁺Doping with MAPBBr₃(ii) a Adjusting the doping concentration of the n-type epitaxial layer 5, forming a space charge layer on the upper part of the n-type epitaxial layer 5, and epitaxially preparing a high-resistance and wide-band-gap perovskite multiplication layer 6, such as MAPbCl, on the n-type epitaxial layer 5 by a solution method₃(ii) a Epitaxially growing a narrow bandgap perovskite multiplication layer 7, such as MAPbBr, on the high resistive wide bandgap perovskite multiplication layer 6₃(ii) a An incident end electrode 2, such as an Au electrode, is vacuum-evaporated at the lower end of the p-type perovskite epitaxial layer 3, and an emergent end electrode 8, such as an Au electrode, is vacuum-evaporated at the upper end of the narrow-band perovskite multiplication layer 7; a power supply is arranged between the incident end electrode 2 and the emergent end electrode 8 to generate reverse bias electricity for the detectorAnd 9, pressing.

In specific implementation, under the action of a reverse bias voltage 9, a certain electric field distribution is generated in the detector, a p-type barrier layer electric field distribution 10 is generated by a p-type perovskite epitaxial layer 3 and used for inhibiting dark-state current, and an x-ray/gamma-ray photon absorption layer electric field distribution 11 is positioned in an ultra-thick intrinsic perovskite photon absorption layer 4 and used for separating photo-generated electron hole pairs.

In a specific implementation, the space charge layer electric field distribution 12 is generated by the n-type perovskite barrier layer and the n + type space charge layer 5 and is used for gradually increasing the electric field intensity and reducing the potential drop of the multiplication layer, and the wide-band gap multiplication region electric field distribution 13 is generated by the high-resistance wide-band gap perovskite multiplication layer 6 and is used for enabling carriers to obtain enough energy and causing avalanche gain through impact ionization.

In particular implementations, the narrow bandgap multiplication region electric field profile 14 is caused by the narrow bandgap perovskite multiplication layer 7 for increasing the multiplication gain.

In specific implementation, based on a typical photocurrent-voltage curve of a high-sensitivity X-ray/gamma-ray detector of a perovskite avalanche transistor, as shown in fig. 5, when the reverse bias 9 reaches an avalanche threshold voltage, the detector can generate a very high signal gain (greater than 100), and the avalanche threshold voltage can be effectively reduced by regulating the concentration and thickness of a space charge layer.

The invention provides a high-sensitivity detection structure based on a perovskite avalanche diode and a preparation method thereof, wherein a metal electrode of the high-sensitivity detection structure adopts a conventional vacuum evaporation method, the preparation processes of intrinsic perovskite crystals and doped epitaxy 49 are shown in figure 6, a growth vessel 39 is placed on a heating table 38, perovskite growth precursor liquid 40 is added, for example, 1mol L of perovskite growth precursor liquid is added^-1MABr of (2), 0.75 mol L^-1PbBr of₂、0.25 mol L^-1PbCl of₂Dissolved in 60 mL DMF, intrinsic perovskite crystals 42 are first obtained in a growth dish 39 by growth 41 by the inverse temperature method, e.g. a small volume of MAPbBr_2.5Cl_0.5The growth time and temperature are controlled to obtain an intrinsic perovskite substrate 43 that meets the design requirements.

Intrinsic perovskite lining formed by solution epitaxial doping methodA p-type or n-type epitaxial layer 46, such as a p-type doped layer, can be grown on the bottom 43, such as MAPbBr₃Adding AgBr salt solution into the precursor solution to grow and form Ag⁺Doped MAPbBr₃The epitaxial layer, but which completely wraps the intrinsic perovskite substrate 43, requires cutting of the crystal along cut-line crystal cuts 47, the resulting epitaxial crystal comprising the cut intrinsic perovskite substrate 48 and the doped epitaxial layer 49.

In the present invention, unless otherwise expressly stated or limited, "above" or "below" a first feature means that the first and second features are in direct contact, or that the first and second features are not in direct contact but are in contact with each other via another feature therebetween. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.