CN110357155A - A kind of X-ray detection X material and application thereof and device - Google Patents
A kind of X-ray detection X material and application thereof and device Download PDFInfo
- Publication number
- CN110357155A CN110357155A CN201910518859.4A CN201910518859A CN110357155A CN 110357155 A CN110357155 A CN 110357155A CN 201910518859 A CN201910518859 A CN 201910518859A CN 110357155 A CN110357155 A CN 110357155A
- Authority
- CN
- China
- Prior art keywords
- ray
- ray detection
- detection
- tabletting
- crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/24—Measuring radiation intensity with semiconductor detectors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Molecular Biology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Measurement Of Radiation (AREA)
Abstract
The invention discloses a kind of X-ray detection X material and application thereof and devices.This X-ray detection X material, general structure A3B2X9, wherein A is Cs, Ag, Rb, NH4One of or a variety of, one of B Bi, Sb or Te or a variety of, X be one of halogen Cl, Br, I or a variety of.The material has high gamma ray absorption coefficient, high carrier service life mobility product, high detectivity, extremely low detectable limit, extraordinary stability, and the critical elements of X-ray detection and imaging can be made.
Description
Technical field
The invention belongs to field of new materials, and in particular to a kind of X-ray and gamma-ray detection material and application thereof and device
Part.
Background technique
X-ray is also known as roentgen-ray, is a kind of wave-length coverage between 0.01 nanometer to 10 nanometers, respective frequencies range
30PHz to 30EHz, the electromagnetic radiation of energy range 100eV to 100KeV.X-ray of the wavelength slightly larger than 0.5nm is referred to as soft X
Ray.What wavelength was shorter than 0.1nm is called hard X ray.Since X-ray is tens times to tens of thousands of times of light photon energy.γ
Ray is a kind of ray more higher than X-ray energy.These properties make its physics, industry and medically obtain it is extensive
Using.
X-ray and gamma-ray penetration are very strong, and when with matter interaction, only a part can be inhaled by substance
It receives, residue is penetrated through atom gap, therefore has very strong penetration capacity.Due to its penetration power and the close phase of material density
Close, thus using different material absorption difference can the substance different to density distinguish.X-ray baggage check instrument is exactly
Based on this principle, it is widely used in security field.Medically, the technologies such as CT based on x-ray imaging, to medical diagnosis on disease
There is huge help with treatment, becomes a specialism already, occupied an important position in field of biomedicine.In medical imaging and
Industrial flaw detection field, gamma-rays equally play great function, for example, PET (positron e mission computed tomography) at
As core element is exactly gamma ray detector.
Under above-mentioned various application occasions, X-ray and gamma-ray detection are all key links therein, therefore X-ray
No matter detector suffers from important value in scientific research or industrial production.Mainly have directly to the detection of high-energy ray
With indirect two classes method, indirect method is to convert ray to after visible light signal by scintillator to be detected with photodetector；Directly
Connection is then that ray is directly changed into electric current.Transverse direction based on the detector array of scintillator due to scintillation light in conversion layer
Diffusion has limited spatial resolution.Therefore, research Direct-type solid state semiconductor detector has more importantly meaning,
Also it will become the core element of the following high-resolution X-ray imaging.
It is well known that high-energy ray has unique biological effect, the interaction with organism can make biological cell
Be suppressed, destroy so necrosis, can make body that the change of different degrees of physiology, pathology and biochemistry etc. occur.This
Although a characteristic can be used on the treatment for the treatment of human body diseases, especially tumour, X-ray can also be led but then
The problem of causing the radiohazards such as alopecia, skin burn, vision disorder and leukaemia.Therefore, in the application of all kinds of imagings and detection
The middle dosage for reducing ray also becomes the target of scientific circles and industry long-sought, and this kind proposed by the present invention penetrates high energy
Line has the material of high sensitivity detection performance, precisely in order to solving this matter of science and technology.Most widely used at present X is penetrated
Line detector is the scheme based on indirect detection, and the program needs the fluorescent powder flashed, is first converted to x-ray photon visible
Light photon, is then detected by photodiode.One better way be X-ray radiation is converted directly into electric signal because
It will make system configuration simpler, have higher spatial resolution.The X-ray detection and imaging system of Direct-type detection at present
Seldom, most of business machine is still detected using silicon, and silicon detector is to X-ray and insensitive, it usually needs very big
Dosage could be imaged, when detected object is the living bodies such as humans and animals, this is a very big healthy hidden danger.The present invention mentions
This kind of material and device that may be used as X-ray detection out, can integrate into imaging system, greatly improves x-ray imaging
Sensitivity reduces dose of radiation required for being imaged.
Summary of the invention
The object of the present invention is to provide a kind of novel to have with high detection sensitivity, low detection dosage, high stability, nothing
The X-ray and gamma-ray detection material of malicious element.
X-ray detection X material provided by the invention, general structure A3B2X9, wherein A is Cs, Ag, Rb, NH4In one
Kind or a variety of, one of B Bi, Sb or Te or a variety of, X are one of halogen Cl, Br, I or a variety of.
Preferably, A3B2X9Middle one kind effect preferably material structure general formula is (NH4)3Bi2I9。
It is this kind of that there is (A3B2X9) type general structure material, usually with 2 dimension or 0 dimension crystal structure, represent one
Major class material system.We have found that having this general structure A3B2X9Material its all have to X-ray and gamma-rays it is good
Detection performance.X-ray and gamma-rays are the electromagnetic waves of different-energy, and the two has similar physical property, are all had relatively strong
Penetration capacity, therefore be also to the performance requirement of detection material it is similar, general good X-ray material is also gamma-ray spy
It measures and monitor the growth of standing timber material.The two requires that the element of constituent material has larger atomic number, big crystalline density, Direct-type detection is come
It says, it is also necessary to high current transfer rate and the product in service life, so that the carrier generated is defeated as soon as possible under DC Electric Field
Electric current both ends are transported to, to realize detecting function.
In addition, the element molecular weight for constituting this kind of material is larger greatly, while density of material is also bigger, in α=Z4/E3's
Under relationship, α is x-ray attenuation coefficient, E is x-ray photon energy, the high X-ray absorption coefficient of collateral security.In addition, this kind of material
Manufacture craft cost is extremely low, is easy to be fabricated to the X-ray plane detection device of large area.Generally speaking this kind of material is in addition to excellent
X-ray absorption and detection performance other than, the process characteristic that is also equipped in following processing: (1) can be using the solution of low cost
Method can easily obtain large single crystal, and size is easy to amplify；(2) crystal has the characteristic of the easy cleavage of two-dimensional layered structure,
It is easy to machine cuts, it is easy to operate.In view of above-mentioned all features, it is believed that this kind of material is expected to excellent as a kind of performance
Good, low in cost, environmentally protective X-ray detector.
Another object of the present invention is to provide a kind of preparation method of X-ray detection X material, preparation process is as follows:
Firstly, by the oxide B containing element B2O3, elements A halide salt AX, be dissolved in the acid solution HX containing element X
In, mixed solution is obtained after dissolution is sufficiently stirred；Wherein A is Cs, Ag, Rb, NH4One of or a variety of, B Bi, Sb or Te
One of or it is a variety of, X is one of halogen Cl, Br, I or a variety of；
Then mixed solution is heated, obtains concentrate solution by being concentrated by evaporation；
Finally, concentrate solution is transferred in the heating furnace of constant temperature, crystal growth is realized, obtain X-ray detection X material
A3B2X9。
Preferably, the time of crystal growth is 2 days or more, and time more long crystal is bigger.
Another object of the present invention is to provide a kind of X-ray detection X materials that above-mentioned preparation method is prepared.
X-ray detection X material in aforementioned each implementation can be used as X-ray detection material, gamma-ray detection material
Material, and X-ray detector, gamma ray detector, X-ray detection imaging device and gamma-rays are further prepared based on these materials
Detecting and imaging device.
The present invention in terms of existing technologies, has the advantages that provided by the invention with layered crystal knot
The X-ray and gamma-ray detection material of structure have high gamma ray absorption coefficient, high carrier service life mobility product, high
Detectivity, extremely low detectable limit, extraordinary stability, can be made the critical elements of X-ray detection and imaging.
Detailed description of the invention
Fig. 1 is with A3B2X9The structure chart of the crystal of structure；
Fig. 2 is a kind of typical (NH4)3Bi2I9Crystal schematic diagram；
Fig. 3 is the X-ray detection device structural schematic diagram based on this kind of material；
Fig. 4 is the X-ray absorption ability schematic diagram of the X-ray detection device based on this kind of material；
Fig. 5 is the lowest detection limit (signal-to-noise ratio corresponding x-ray dose when being 3) of X-ray detector；
Fig. 6 is the lowest detection limit (signal-to-noise ratio corresponding x-ray dose when being 3) of X-ray detector；
Fig. 7 is the lowest detection limit (signal-to-noise ratio corresponding x-ray dose when being 3) of X-ray detector；
Fig. 8 is the current-responsive when X-ray opens and closes of X-ray detector；
Fig. 9 is the current-responsive when X-ray opens and closes of X-ray detector；
Figure 10 is the current-responsive when X-ray opens and closes of X-ray detector；
Figure 11 is the current-responsive when X-ray opens and closes of X-ray detector.
Specific embodiment
The present invention is further elaborated and is illustrated with reference to the accompanying drawings and detailed description.
For the X-ray detection X material in the present invention, it has been found that this kind of material suitable for high-energy ray detection has
(A3B2X9) type general structure, B location is the metal or metalloid element of trivalent, can be Bi, Sb or Te or trivalent
The combination of cation.It is wherein non-evergreen color and stable metallic element with Bi bismuth element.Location A can be Cs, Ag, Rb, NH4
Equal monovalent cations, or the wherein combination of any 2 kinds or two or more monovalent cation；X position can be Cl, Br, I halogen
The combination of a kind of or any two kinds, three kinds halogen atoms in prime element.
Wherein, the present invention also provides a kind of preparation method of such X-ray detection X material, detailed processes are as follows:
Firstly, by the oxide B containing element B2O3, elements A halide salt AX, be dissolved in the acid solution HX containing element X
In, mixed solution is obtained after dissolution is sufficiently stirred；Wherein A is Cs, Ag, Rb, NH4One of or a variety of, B Bi, Sb or Te
One of or it is a variety of, X is one of halogen Cl, Br, I or a variety of；
Then mixed solution is heated, obtains concentrate solution by being concentrated by evaporation；
Finally, concentrate solution is transferred in the heating furnace of constant temperature, crystal growth is realized, obtain X-ray detection X material
A3B2X9。
The present invention is illustrated below by specific embodiment.Reagent employed in various embodiments of the present invention,
Material, if commercially available material can be used without specified otherwise.Acid solutions refer both to mass percent in each embodiment.
Embodiment 1
By 1g bismuth oxide (Bi2O3) and 2.5 grams of iodate ammonia be dissolved in the hydroiodic acid that 5ml concentration is 45%, at room temperature
After being stirred overnight, obtained solution is placed on hot plate, in 110 DEG C of heating evaporations and is concentrated.Then concentrate solution is rapid
It is transferred in heating furnace, the crystal growth under 60 DEG C of constant temperature obtains crystalline material (NH4)3Bi2I9.Take out the crystal grown simultaneously
Silver electrode is coated on the whole, forms Ag/ (NH4)3Bi2I9/ Ag structure, wherein metal electrode can be arbitrary gold, silver, copper,
The electric conductors such as aluminium, such device can be used for X-ray detection.Other than utilization such monocrystalline detection, it can also incite somebody to action
Crystal crushes, tabletting is fabricated to polycrystalline tabletting, the depositing electrode in tabletting, be fabricated to based on polycrystalline X-ray detector or
Imaging array.
Embodiment 2
1g bismuth oxide and 2.5 grams of ammonia bromide are dissolved in the hydrobromic acid that 5ml concentration is 45%, are stirred at room temperature one
Obtained solution is placed on hot plate after night, in 110 DEG C of heating evaporations and is concentrated.Then concentrate solution is quickly transferred to add
Hot stove, the crystal growth under 60 DEG C of constant temperature obtain crystalline material (NH4)3Bi2Br9.It takes out the crystal grown and applies on the whole
Upper silver electrode forms Ag/ (NH4)3Bi2Br9/ Ag structure, wherein metal electrode can be arbitrary gold, silver, copper, aluminium etc. and lead
Electric body, such device can be used for X-ray detection.It, can also be by crystal powder other than using the detection of such monocrystalline
Broken, tabletting is fabricated to polycrystalline tabletting, the depositing electrode in tabletting, is fabricated to based on polycrystalline X-ray detector or imaging battle array
Column.
Embodiment 3
1g bismuth oxide and 2.5 grams of ammonia bromide are dissolved in the hydrobromic acid and hydroiodic acid mixed solution that 5ml concentration is 45%
(HBr:HI=1:1) it in, is stirred at room temperature after a night and obtained solution is placed on hot plate, simultaneously in 110 DEG C of heating evaporations
Concentration.Then concentrate solution is quickly transferred to heating furnace, the crystal growth under 60 DEG C of constant temperature obtains crystalline material (NH4)3Bi2Br4.5I4.5.It takes out the crystal grown and coats silver electrode on the whole, form Ag/ (NH4)3Bi2Br4.5I4.5/ Ag structure,
Wherein metal electrode can be arbitrary the electric conductors such as gold, silver, copper, aluminium, and such device can be used for X-ray detection.It removes
Other than the detection of such monocrystalline, crystal can also be crushed, tabletting be fabricated to polycrystalline tabletting, electricity is deposited in tabletting
Pole is fabricated to based on polycrystalline X-ray detector or imaging array.
Embodiment 4
1g bismuth oxide and 2.5 grams of ammonia bromide are dissolved in the hydrochloric acid that 5ml concentration is 45%, a night is stirred at room temperature
Obtained solution is placed on hot plate later, in 110 DEG C of heating evaporations and is concentrated.Then concentrate solution is quickly transferred to heat
Furnace, the crystal growth under 60 DEG C of constant temperature obtain crystalline material (NH4)3Bi2Cl9.It takes out the crystal grown and coats on the whole
Silver electrode forms Ag/ (NH4)3Bi2Cl9/ Ag structure, wherein metal electrode can be arbitrary the conductions such as gold, silver, copper, aluminium
Body, such device can be used for X-ray detection.Other than using the detection of such monocrystalline, crystal can also be crushed,
Tabletting is fabricated to polycrystalline tabletting, and the depositing electrode in tabletting is fabricated to based on polycrystalline X-ray detector or imaging array.
Embodiment 5
By the mixture (ammonium iodide: ammonium bromide: ammonium chloride of 0.8g bismuth oxide and 2.0 grams of ammonium iodides, ammonium bromide and ammonium chloride
=1:1:1) it is dissolved in the hydrobromic acid that 5ml concentration is 45%, the mixed liquor (HBr:HI:HCl=1:1:1) of hydroiodic acid and hydrochloric acid
In, it is stirred at room temperature after a night and obtained solution is placed on hot plate, in 110 DEG C of heating evaporations and be concentrated.It then will be dense
Contracting solution is quickly transferred to heating furnace, and the crystal growth under 60 DEG C of constant temperature obtains crystalline material (NH4)3Bi2Cl3Br3I3.It takes
The crystal that the grows out and device that silver electrode is deposited on the whole forms Ag/ (NH4)3Bi2Cl3Br3I3/ Ag structure, wherein metal
Electrode can be arbitrary the electric conductors such as gold, silver, copper, aluminium, and such device can be used for X-ray detection.In addition to utilizing this
Other than the monocrystalline detection of sample, crystal can also be crushed, tabletting is fabricated to polycrystalline tabletting, the depositing electrode in tabletting, production
At based on polycrystalline X-ray detector or imaging array.The ratio of HI, HBr and hydrochloric acid can change, Cl, Br and I in reactant
It will affect the halogen ratio of end product.
Embodiment 6
1g bismuth oxide and 2.5 grams of cesium iodide are dissolved in the hydroiodic acid that 5ml concentration is 45%, are stirred at room temperature one
Obtained solution is placed on hot plate after night, in 110 DEG C of heating evaporations and is concentrated.Then concentrate solution is quickly transferred to add
Hot stove, the crystal growth under 60 DEG C of constant temperature obtain crystalline material Cs3Bi2I9.It takes out the crystal grown and coats silver on the whole
Electrode forms Ag/Cs3Bi2I9/ Ag structure, wherein metal electrode can be arbitrary the electric conductors such as gold, silver, copper, aluminium, in this way
Device can be used for X-ray detection.Other than using the detection of such monocrystalline, crystal can also be crushed, tabletting system
It is made polycrystalline tabletting, the depositing electrode in tabletting is fabricated to based on polycrystalline X-ray detector or imaging array.
Embodiment 7
By 0.8g antimony oxide (Sb2O3) and 2.5 grams of iodate ammonia be dissolved in the hydroiodic acid that 5ml concentration is 45%, in room temperature
Under be stirred overnight after obtained solution is placed on hot plate, in 110 DEG C of heating evaporations and be concentrated.Then concentrate solution is rapid
It is transferred to heating furnace, the crystal growth under 60 DEG C of constant temperature obtains crystalline material (NH4)3Sb2I9.Take out the crystal that grows and
The device that silver electrode is deposited on face forms Ag/ (NH4)3Sb2I9/ Ag structure, wherein metal electrode can be arbitrary gold, silver,
The electric conductors such as copper, aluminium, such device can be used for X-ray detection.It, can also be with other than using the detection of such monocrystalline
Crystal crushing, tabletting are fabricated to polycrystalline tabletting, the depositing electrode in tabletting is fabricated to based on polycrystalline X-ray detector
Or imaging array.
Embodiment 8
0.4g bismuth oxide, 0.4g antimony oxide and 2.0 grams of iodate ammonia are dissolved in the hydroiodic acid that 5ml concentration is 45%,
It is stirred at room temperature overnight, obtained solution is placed on hot plate later, in 110 DEG C of heating evaporations and be concentrated.It then will concentration
Solution is quickly transferred to heating furnace, and the crystal growth under 60 DEG C of constant temperature obtains crystalline material (NH4)3BiSbI9.Taking-up is grown
Crystal and on the whole be deposited silver electrode device form Ag/ (NH4)3BiSbI9/ Ag structure, wherein metal electrode can be
Electric conductors, such devices such as arbitrary gold, silver, copper, aluminium can be used for X-ray detection.In addition to being visited using such monocrystalline
Other than survey, crystal crushing, tabletting can also be fabricated to polycrystalline tabletting, the depositing electrode in tabletting is fabricated to based on polycrystalline
X-ray detector or imaging array.
Embodiment 9
0.8g bismuth oxide and 2.0 grams of silver iodide are dissolved in the hydroiodic acid that 5ml concentration is 45%, are stirred at room temperature
Overnight, obtained solution is placed on hot plate later, in 110 DEG C of heating evaporations and is concentrated.Then concentrate solution is shifted rapidly
To heating furnace, the crystal growth under 60 DEG C of constant temperature obtains crystalline material (Ag)3Bi2I9.Take out the crystal that grows and on the whole
The device of vapor deposition silver electrode forms Ag/ (Ag)3Bi2I9/ Ag structure, wherein metal electrode can be arbitrary gold, silver, copper, aluminium
Equal electric conductors, such device can be used for X-ray detection.It, can also will be brilliant other than using the detection of such monocrystalline
Body crush, tabletting be fabricated to polycrystalline tabletting, the depositing electrode in tabletting, be fabricated to based on polycrystalline X-ray detector or at
As array.
Embodiment 10
0.8g bismuth oxide and 1.0 grams of silver iodide, 1.0 grams of silver bromides are dissolved in the hydroiodic acid and hydrogen that 5ml concentration is 45%
In the mixed liquor (HI:HBr=1:1) of bromic acid, it is stirred at room temperature overnight, obtained solution is placed on hot plate later, in 110
DEG C heating evaporation is simultaneously concentrated.Then concentrate solution is quickly transferred to heating furnace, the crystal growth under 60 DEG C of constant temperature obtains crystalline substance
Body material (Ag)3Bi2I4.5Br4.5.It takes out the crystal grown and the device that silver electrode is deposited on the whole forms Ag/ (Ag)3Bi2I4.5Br4.5/ Ag structure, wherein metal electrode can be arbitrary the electric conductors such as gold, silver, copper, aluminium, such device
To be used for X-ray detection.Other than using the detection of such monocrystalline, crystal can also be crushed, tabletting is fabricated to polycrystalline
Tabletting, the depositing electrode in tabletting are fabricated to based on polycrystalline X-ray detector or imaging array.
Embodiment 11
0.8g bismuth oxide and 1.2 grams of ammonium iodides, 0.8 gram of silver iodide are dissolved in the hydroiodic acid that 5ml concentration is 45%,
It is stirred overnight, obtained solution is placed on hot plate at room temperature later, in 110 DEG C of heating evaporations and be concentrated.Then it will be concentrated molten
Liquid is quickly transferred to heating furnace, the crystal growth under 60 DEG C of constant temperature, obtains crystalline material Ag (NH4)2Bi2I9.What taking-up was grown
Crystal and on the whole be deposited silver electrode device form Ag/Ag (NH4)2Bi2I9/ Ag structure, wherein metal electrode, which can be, appoints
The electric conductors such as gold, silver, copper, the aluminium of meaning, such device can be used for X-ray detection.In addition to being detected using such monocrystalline
In addition, crystal crushing, tabletting can also be fabricated to polycrystalline tabletting, the depositing electrode in tabletting is fabricated to based on polycrystalline X
Ray detector or imaging array.
Embodiment 12
0.8g antimony oxide and 2.5 grams of rubidium iodide are dissolved in the hydroiodic acid that 5ml concentration is 45%, are stirred at room temperature
Obtained solution is placed on hot plate after one night, in 110 DEG C of heating evaporations and is concentrated.Then concentrate solution is quickly transferred to
Heating furnace, the crystal growth under 60 DEG C of constant temperature obtain crystalline material (Rb)3Sb2I9.It takes out the crystal grown and steams on the whole
The device of silver-coated electrode forms Ag/ (Rb)3Sb2I9/ Ag structure, wherein metal electrode can be arbitrary gold, silver, copper, aluminium etc.
Electric conductor, such device can be used for X-ray detection.It, can also be by crystal other than using the detection of such monocrystalline
Crushing, tabletting are fabricated to polycrystalline tabletting, and the depositing electrode in tabletting is fabricated to based on polycrystalline X-ray detector or imaging
Array.
Embodiment 13
0.8g antimony oxide and 2.0 grams of ammonium iodide are dissolved in the hydroiodic acid that 5ml concentration is 45%, are stirred at room temperature
Obtained solution is placed on hot plate after one night, in 110 DEG C of heating evaporations and is concentrated.Then concentrate solution is quickly transferred to
Heating furnace, the crystal growth under 60 DEG C of constant temperature obtain crystalline material (NH4)3Sb2I9.It takes out the crystal grown and steams on the whole
The device of silver-coated electrode forms Ag/ (NH4)3Sb2I9/ Ag structure, wherein metal electrode can be arbitrary gold, silver, copper, aluminium
Equal electric conductors, such device can be used for X-ray detection.It, can also will be brilliant other than using the detection of such monocrystalline
Body crush, tabletting be fabricated to polycrystalline tabletting, the depositing electrode in tabletting, be fabricated to based on polycrystalline X-ray detector or at
As array.
Embodiment 14
0.8g antimony oxide and 2.0 grams of ammonium iodide are dissolved in the hydrochloric acid that 5ml concentration is 25%, are stirred at room temperature one
Obtained solution is placed on hot plate after night, in 110 DEG C of heating evaporations and is concentrated.Then concentrate solution is quickly transferred to add
Hot stove, the crystal growth under 60 DEG C of constant temperature obtain crystalline material (NH4)3Sb2Cl9.It takes out the crystal grown and steams on the whole
The device of silver-coated electrode forms Ag/ (NH4)3Sb2Cl9/ Ag structure, wherein metal electrode can be arbitrary gold, silver, copper, aluminium
Equal electric conductors, such device can be used for X-ray detection.It, can also will be brilliant other than using the detection of such monocrystalline
Body crush, tabletting be fabricated to polycrystalline tabletting, the depositing electrode in tabletting, be fabricated to based on polycrystalline X-ray detector or at
As array.
Embodiment 15
0.8g antimony oxide and 2.0 grams of ammonium iodide are dissolved in the hydrobromic acid that 5ml concentration is 45%, are stirred at room temperature
Obtained solution is placed on hot plate after one night, in 110 DEG C of heating evaporations and is concentrated.Then concentrate solution is quickly transferred to
Heating furnace, the crystal growth under 60 DEG C of constant temperature obtain crystalline material (NH4)3Sb2Br9.Take out the crystal that grows and on the whole
The device of vapor deposition silver electrode forms Ag/ (NH4)3Sb2Br9/ Ag structure, wherein metal electrode can be arbitrary gold, silver, copper,
The electric conductors such as aluminium, such device can be used for X-ray detection.Other than utilization such monocrystalline detection, it can also incite somebody to action
Crystal crushes, tabletting is fabricated to polycrystalline tabletting, the depositing electrode in tabletting, be fabricated to based on polycrystalline X-ray detector or
Imaging array.
Embodiment 16
0.8g antimony oxide and 2.0 grams of ammonium iodide are dissolved in the hydrobromic acid and hydroiodic acid mixed liquor that 5ml concentration is 45%
(HBr:HI=1:1) it in, is stirred at room temperature after a night and obtained solution is placed on hot plate, simultaneously in 110 DEG C of heating evaporations
Concentration.Then concentrate solution is quickly transferred to heating furnace, the crystal growth under 60 DEG C of constant temperature obtains crystalline material (NH4)3Sb2Br4.5I4.5.It takes out the crystal grown and the device that silver electrode is deposited on the whole forms Ag/ (NH4)3Sb2Br4.5I4.5/Ag
Structure, wherein metal electrode can be arbitrary the electric conductors such as gold, silver, copper, aluminium, and such device can be used for X-ray inspection
It surveys.Other than using the detection of such monocrystalline, crystal crushing, tabletting can also be fabricated to polycrystalline tabletting, in tabletting
Depositing electrode is fabricated to based on polycrystalline X-ray detector or imaging array.The ratio of HI and HBr can change, in reactant
Br and I will affect the halogen ratio of end product.
Embodiment 17
0.8g antimony oxide and 2.0 grams of ammonium iodide are dissolved in hydrobromic acid, hydroiodic acid and the hydrochloric acid that 5ml concentration is 45%
In mixed liquor (HBr:HI:HCl=1:1:1), it is stirred at room temperature after a night and obtained solution is placed on hot plate, in 110
DEG C heating evaporation is simultaneously concentrated.Then concentrate solution is quickly transferred to heating furnace, the crystal growth under 60 DEG C of constant temperature obtains crystalline substance
Body material (NH4)3Sb2Cl3Br3I3.It takes out the crystal grown and the device that silver electrode is deposited on the whole forms Ag/ (NH4)3Sb2Cl3Br3I3/ Ag structure, wherein metal electrode can be arbitrary the electric conductors such as gold, silver, copper, aluminium, such device
To be used for X-ray detection.Other than using the detection of such monocrystalline, crystal can also be crushed, tabletting is fabricated to polycrystalline
Tabletting, the depositing electrode in tabletting are fabricated to based on polycrystalline X-ray detector or imaging array.The ratio of HI, HBr and hydrochloric acid
Example can change, and Cl, Br and I will affect the halogen ratio of end product in reactant.
There is (A in above-described embodiment3B2X9) type general structure material, all show the spy preferably to X-ray
Performance is surveyed, device electric current when receiving X-ray irradiation can occur significantly to change.The material of part of embodiment preparation is taken below
Material is used as Typical Representative, is shown by following embodiments to its effect.
Embodiment 18
(the NH synthesized with embodiment 14)3Bi2I9For Typical Representative, material and sensitive detection parts essential characteristic such as attached drawing 1-5
It is shown.It is the crystal structure schematic diagram of this kind of material shown in Fig. 1, shows its crystal structure with stratiform, and be relatively easy
The crystal of larger size is prepared by simple hydro-thermal method, macro morphology is as shown in Figure 2.In such crystal two sides, sink
This kind of photoconduction type X-ray detection with sandwich structure of metal, semiconductor, metal can be formed after product metal electrode
Device, as shown in Figure 3.Fig. 4 shows that this material is noticeably greater than conventional silicon materials to the absorption coefficient of X-ray, same
Under thickness, high several times even several orders of magnitude are wanted to the abatement coefficient ratio silicon of X-ray.This means that being penetrated reaching same X
Line absorption effect, the detection material that we use is thinner than traditional material very much, this not only saves cost, while more importantly
The transition time of such device, electrons and holes is shorter, can obtain higher photoelectric conversion efficiency, and Fig. 5 shows this kind of
Device be only 55nG to the lowest detection limit of X-rayair, this index 2-3 quantity better than current commercial system
Grade, is one thousandth of medical standard or so.
Embodiment 19
(the NH synthesized with embodiment 24)3Bi2Br9For another Typical Representative, material and sensitive detection parts essential characteristic are such as
Shown in attached drawing 6.This material is equally noticeably greater than conventional silicon materials to the absorption coefficient of X-ray, because of the atomic number of Br
It is smaller than I, thus it is more smaller than the material of embodiment 1, under same thickness, several times high is wanted to the abatement coefficient ratio silicon of X-ray
Even several orders of magnitude.This means that the detection material that we use compares traditional material reaching same X-ray absorption effect
Want it is thin much this not only saves cost, while more importantly such device, the transition time of electrons and holes is shorter,
Higher photoelectric conversion efficiency can be obtained, Fig. 6 shows that this kind of device is only 210nG to the lowest detection limit of X-rayair,
This index is the one thousandth of medical standard to 1 percent or so than current 2 orders of magnitude of commercial system.
Embodiment 19
Ag (the NH synthesized with embodiment 114)2Bi2I9For another Typical Representative, material and sensitive detection parts essential characteristic
As shown in Fig. 7.This material is equally noticeably greater than conventional silicon materials to the absorption coefficient of X-ray, under same thickness,
It wants high several times even several orders of magnitude to the abatement coefficient ratio silicon of X-ray.This means that reaching same X-ray absorption effect
Fruit, the detection material that we use is thinner than traditional material very much, this not only saves cost, while more importantly such device
The transition time of part, electrons and holes is shorter, can obtain higher photoelectric conversion efficiency, and Fig. 7 shows this kind of device to X
The lowest detection limit of ray is only 120nGair, this index is medical mark than current 2 orders of magnitude of commercial system
Quasi- one thousandth is to 1 percent or so.
Embodiment 19
(Rb) synthesized with embodiment 123Sb2I9For another Typical Representative, material and sensitive detection parts essential characteristic are such as
Shown in attached drawing 8.This material is equally noticeably greater than conventional silicon materials to the absorption coefficient of X-ray, under same thickness,
High several times even several orders of magnitude are wanted to the abatement coefficient ratio silicon of X-ray.This means that reaching same X-ray absorption effect
Fruit, the detection material that we use is thinner than traditional material very much, this not only saves cost, while more importantly such device
The transition time of part, electrons and holes is shorter, can obtain higher photoelectric conversion efficiency, and Fig. 8 shows this kind of device to X
Ray has apparent response, and after illumination X-ray, device current is obviously bigger than under dark-state, is a kind of excellent X-ray detection material
Material.
Embodiment 20
(Ag) synthesized with embodiment 103Bi2I4.5Br4.5For another Typical Representative, material and sensitive detection parts are substantially special
Sign is as shown in Fig. 9.This material is equally noticeably greater than conventional silicon materials to the absorption coefficient of X-ray, in same thickness
Under, high several times even several orders of magnitude are wanted to the abatement coefficient ratio silicon of X-ray.This means that being inhaled reaching same X-ray
It produces effects fruit, the detection material that we use is thinner than traditional material very much, this not only saves cost, while more importantly in this way
Device, the transition time of electrons and holes is shorter, can obtain higher photoelectric conversion efficiency, and Fig. 9 shows this kind of device
Part has apparent response to X-ray, and after illumination X-ray, device current is obviously bigger than under dark-state, is a kind of excellent X-ray
Detect material.
Embodiment 20
(Ag) synthesized with embodiment 103Bi2I4.5Br4.5For another Typical Representative, material and sensitive detection parts are substantially special
Sign is as shown in Fig. 10.This material is equally noticeably greater than conventional silicon materials to the absorption coefficient of X-ray, in same thickness
Under, high several times even several orders of magnitude are wanted to the abatement coefficient ratio silicon of X-ray.This means that being inhaled reaching same X-ray
It produces effects fruit, the detection material that we use is thinner than traditional material very much, this not only saves cost, while more importantly in this way
Device, the transition time of electrons and holes is shorter, can obtain higher photoelectric conversion efficiency, and Figure 10 shows this kind of device
Part has apparent response to X-ray, and after illumination X-ray, device current is obviously bigger than under dark-state, is a kind of excellent X-ray
Detect material.
Embodiment 21
(the NH synthesized with the path of embodiment 144)3Sb2Cl9For another Typical Representative, material and sensitive detection parts base
Eigen is as shown in Fig. 11.This material is equally noticeably greater than conventional silicon materials to the absorption coefficient of X-ray, same
Under thickness, high several times even several orders of magnitude are wanted to the abatement coefficient ratio silicon of X-ray.This means that being penetrated reaching same X
Line absorption effect, the detection material that we use is thinner than traditional material very much, this not only saves cost, while more importantly
The transition time of such device, electrons and holes is shorter, can obtain higher photoelectric conversion efficiency, and Figure 11 shows this kind of
Device have apparent response to X-ray, after illumination X-ray, device current is obviously bigger than under dark-state, is a kind of excellent X
X-ray detection X material.
Embodiment 22
Based on X-ray detection X material made from previous embodiment, X-ray spy can be fabricated to by connecting with metal electrode
Device is surveyed, in x-ray bombardment to device, under the action of bias, X-ray electric current can be generated, external circuitry reads this electric current
It value and is compared with the electric current under dark-state, so that it may detect the presence or absence of X-ray.Certainly, these X-ray detection devices can
With further application integration into complete set of equipments, after this kind of device forming array, can constitute imaging system for X at
The application field of picture, such as human body X light transmission, X-ray Chest X-rays, CT, airport X inspection etc., form chest x-ray machine, CT machine, X
Ray rays safety detection apparatus etc. imaging device.
Moreover, X-ray and gamma-rays are the electromagnetic waves of different-energy, the two has similar physical property, all has
Stronger penetration capacity, thus be also to the performance requirement of detection material it is similar, general good X-ray material is also gamma-rays
Detection material.Although previous embodiment by taking X-ray detection as an example, shows its effect, it also has gamma-rays similar
Effect, therefore can be used as gamma-ray detection material, and be further formed gamma ray detector and gamma-ray detection imaging device.
Above-mentioned embodiment is only a preferred solution of the present invention, so it is not intended to limiting the invention.Have
The those of ordinary skill for closing technical field can also make various changes without departing from the spirit and scope of the present invention
Change and modification.Therefore all mode technical solutions obtained for taking equivalent substitution or equivalent transformation, all fall within guarantor of the invention
It protects in range.
Claims (10)
1. a kind of X-ray detection X material, which is characterized in that general structure A3B2X9, wherein A is Cs, Ag, Rb, NH4One of
Or a variety of, one of B Bi, Sb or Te or a variety of, X are one of halogen Cl, Br, I or a variety of.
2. X-ray detection X material as described in claim 1, which is characterized in that general structure is (NH4)3Bi2I9。
3. a kind of preparation method of X-ray detection X material, which is characterized in that
Firstly, by the oxide B containing element B2O3, elements A halide salt AX, be dissolved in the acid solution HX containing element X,
Mixed solution is obtained after dissolution is sufficiently stirred；Wherein A is Cs, Ag, Rb, NH4One of or it is a variety of, in B Bi, Sb or Te
One or more, X is one of halogen Cl, Br, I or a variety of；
Then mixed solution is heated, obtains concentrate solution by being concentrated by evaporation；
Finally, concentrate solution is transferred in the heating furnace of constant temperature, crystal growth is realized, obtain X-ray detection X materials A3B2X9。
4. a kind of X-ray detection X material that preparation method is prepared according to claim 3.
5. a kind of purposes of the X-ray detection X material as X-ray detection material as described in Claims 1 to 4 is any.
6. a kind of purposes of the X-ray detection X material as gamma-ray detection material as described in Claims 1 to 4 is any.
7. a kind of X-ray detector using any X-ray detection X material manufacture of Claims 1 to 44.
8. a kind of X-ray detection imaging device using any X-ray detection X material manufacture of Claims 1 to 44.
9. a kind of gamma ray detector using any X-ray detection X material manufacture of Claims 1 to 44.
10. a kind of gamma-ray detection imaging device using any X-ray detection X material manufacture of Claims 1 to 44.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910518859.4A CN110357155B (en) | 2019-06-16 | 2019-06-16 | Ray detection material and application and device thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910518859.4A CN110357155B (en) | 2019-06-16 | 2019-06-16 | Ray detection material and application and device thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110357155A true CN110357155A (en) | 2019-10-22 |
| CN110357155B CN110357155B (en) | 2021-01-29 |
Family
ID=68216342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910518859.4A Active CN110357155B (en) | 2019-06-16 | 2019-06-16 | Ray detection material and application and device thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110357155B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160155974A1 (en) * | 2014-12-01 | 2016-06-02 | The Regents Of The University Of California | Complex pnictide metal halides for optoelectronic applications |
| CN106082329A (en) * | 2016-06-12 | 2016-11-09 | 上海科技大学 | A kind of containing bismuth and the semi-conducting material of halogen and preparation thereof and the method for analysis |
| CN107068872A (en) * | 2016-12-08 | 2017-08-18 | 常州大学 | One kind prepares perovskite Cs3Bi2I9The method of hull cell |
| CN108502927A (en) * | 2018-05-29 | 2018-09-07 | 华中科技大学 | A kind of preparation method of caesium bismuth bromine perovskite nanometer sheet |
| CN109052470A (en) * | 2018-10-15 | 2018-12-21 | 郑州大学 | A kind of inorganic non-lead caesium bismuth halogen Cs3Bi2X9Perovskite micron disk and its synthetic method |
| CN109273601A (en) * | 2018-09-06 | 2019-01-25 | 华中科技大学 | A kind of perovskite solar battery and preparation method thereof |
-
2019
- 2019-06-16 CN CN201910518859.4A patent/CN110357155B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160155974A1 (en) * | 2014-12-01 | 2016-06-02 | The Regents Of The University Of California | Complex pnictide metal halides for optoelectronic applications |
| CN106082329A (en) * | 2016-06-12 | 2016-11-09 | 上海科技大学 | A kind of containing bismuth and the semi-conducting material of halogen and preparation thereof and the method for analysis |
| CN107068872A (en) * | 2016-12-08 | 2017-08-18 | 常州大学 | One kind prepares perovskite Cs3Bi2I9The method of hull cell |
| CN108502927A (en) * | 2018-05-29 | 2018-09-07 | 华中科技大学 | A kind of preparation method of caesium bismuth bromine perovskite nanometer sheet |
| CN109273601A (en) * | 2018-09-06 | 2019-01-25 | 华中科技大学 | A kind of perovskite solar battery and preparation method thereof |
| CN109052470A (en) * | 2018-10-15 | 2018-12-21 | 郑州大学 | A kind of inorganic non-lead caesium bismuth halogen Cs3Bi2X9Perovskite micron disk and its synthetic method |
Non-Patent Citations (5)
| Title |
|---|
| CHUANTIAN ZUO ET AL.: "Lead-free Perovskite Materials (NH4)3Sb2IxBr9-x", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
| JEN-HUI CHANG ET AL.: "Structural Variety of Defect Perovskite Variants M3E2X9 (M=Rb，Tl，E = Bi，Sb，X = Br，I)", 《ZEITSCHRIFT FÜR ANORGANISCHE UND ALLGEMEINE CHEMIE》 * |
| KYLE M. MCCALL ET AL.: "α‑Particle Detection and Charge Transport Characteristics in the A3M2I9 Defect Perovskites (A=Cs，Rb；M =Bi，Sb)", 《ACS PHOTONICS》 * |
| QIHAO SUN ET AL.: "Optical and electronic anisotropies in perovskitoid crystals of Cs3Bi2I9 studies of nuclear radiation detection", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| SHIJING SUN ET AL.: "Synthesis，crystal structure，and properties of a perovskite-related bismuth phase，(NH4)3Bi2I9", 《APL MATERIALS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110357155B (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Su et al. | Perovskite semiconductors for direct X-ray detection and imaging | |
| US9835737B1 (en) | Autonomous gamma, X-ray, and particle detector | |
| Li et al. | Ultralow detection limit and robust hard X-ray imaging detector based on inch-sized lead-free perovskite Cs3Bi2Br9 single crystals | |
| Li et al. | Zero-dimensional lead-free FA3Bi2I9 single crystals for high-performance X-ray detection | |
| Ma et al. | Highly efficient NaGdF4: Ce/Tb nanoscintillator with reduced afterglow and light scattering for high-resolution X-ray imaging | |
| Mao et al. | Organic–inorganic hybrid cuprous halide scintillators for flexible X-ray imaging | |
| US5821541A (en) | Method and apparatus for radiation detection | |
| Wu et al. | One-dimensional scintillator film with benign grain boundaries for high-resolution and fast x-ray imaging | |
| Ariño-Estrada et al. | First Cerenkov charge-induction (CCI) TlBr detector for TOF-PET and proton range verification | |
| Lin et al. | TlSn2I5, a robust halide antiperovskite semiconductor for γ-ray detection at room temperature | |
| Ou et al. | X-ray nanocrystal scintillator-based aptasensor for autofluorescence-free detection | |
| Ma et al. | Centimeter-sized 2D perovskitoid single crystals for efficient X-ray photoresponsivity | |
| Yang et al. | Performance comparison of two signal multiplexing readouts for SiPM-based pet detector | |
| Yang et al. | Recent advances in radiation detection technologies enabled by metal-halide perovskites | |
| Hu et al. | Perovskite semiconductors for ionizing radiation detection | |
| Heo et al. | Self-powered flexible all-perovskite X-ray detectors with high sensitivity and fast response | |
| Yao et al. | Visualization of X-rays with an ultralow detection limit via zero-dimensional perovskite scintillators | |
| Qiu et al. | Polymer composites entrapped Ce-doped LiYF4 microcrystals for high-sensitivity X-ray scintillation and imaging | |
| Wang et al. | Cs3Cu2I5 perovskite nanoparticles in polymer matrix as large-area scintillation screen for high-definition X-ray imaging | |
| Michail et al. | Absolute luminescence efficiency of europium-doped calcium fluoride (CaF2: Eu) single crystals under X-ray excitation | |
| Onoda et al. | Photoluminescence and scintillation properties of (C 6 H 5 C 2 H 4 NH 3) 2 Pb 1− x Zn x Br 4 as a two-dimensional quantum-confined scintillator | |
| Nakauchi et al. | X-and γ-ray response of Sm-doped SrBr2 crystalline scintillators emitting red-NIR photons | |
| Xu et al. | A preclinical PET detector constructed with a monolithic scintillator ring | |
| Ichiba et al. | X-ray-Induced scintillation properties of nd-doped bi4si3o12 crystals in visible and near-infrared regions | |
| Li et al. | A Thermoplastic Organic Metal Halide Scintillator |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |