阅读说明：本技术 一种基于铋硒碲薄膜材料的光、热探测器及其制备方法 (Light and heat detector based on bismuth-selenium-tellurium film material and preparation method thereof ) 是由 马继奎 王淑芳 陈明敬 方立德 李红莲 李小亭 傅广生 于 2020-03-03 设计创作，主要内容包括：本发明提供了一种基于铋硒碲薄膜材料的光、热探测器及其制备方法,光、热探测器包括横向热电元件、金属电极及金属引线,在横向热电元件的上表面设置有两个对称的金属电极,金属引线与金属电极相连接；横向热电元件包括铋硒碲薄膜,该铋硒碲薄膜沿<I>c</I>轴倾斜生长在斜切氧化物单晶基片上。本发明探测器的探测元件结构简单、制备方法简便、成本低廉,所得光、热探测器探测光谱波段宽,探测灵敏度高,响应时间快,且可探测各种热辐射,应用前景广阔。(The invention provides a light and heat detector based on a bismuth-selenium-tellurium film material and a preparation method thereof, wherein the light and heat detector comprises a transverse thermoelectric element, metal electrodes and metal leads, two symmetrical metal electrodes are arranged on the upper surface of the transverse thermoelectric element, and the metal leads are connected with the metal electrodes; the transverse thermoelectric element comprises a bismuth-selenium-tellurium film c The axis is grown obliquely on a chamfered oxide single crystal substrate. The detection element of the detector has the advantages of simple structure, simple and convenient preparation method and low cost, and the obtained optical and thermal detector has wide detection spectrum wave band, high detection sensitivity, quick response time, capability of detecting various thermal radiation and wide application prospect.)

1. A light and heat detector based on a bismuth-selenium-tellurium film material comprises a transverse thermoelectric element, metal electrodes and metal leads, and is characterized in that the upper surface of the transverse thermoelectric element is provided with two symmetrical metal electrodes, the metal electrodes are used for collecting voltage, and the metal leads are connected with the metal electrodes and used for transmitting voltage signals; the transverse thermoelectric element comprises a bismuth-selenium-tellurium filmcThe axis is grown obliquely on a chamfered oxide single crystal substrate.

2. The light and heat detector based on the bismuth-selenium-tellurium film material as claimed in claim 1, wherein the thickness of the bismuth-selenium-tellurium film is 30-150 nm.

3. The optical/thermal detector of claim 1, wherein the beveled oxide single crystal substrate is a bismuth-selenium-tellurium thin filmcThe shaft beveling angle theta is 0 DEG<θ<30°。

4. The light and heat detector based on bismuth-selenium-tellurium thin film material as claimed in claim 1, wherein the oxide single crystal substrate is lanthanum aluminate, strontium titanate, strontium-tantalum lanthanum aluminate, magnesium oxide or sapphire.

5. The light and heat detector based on bismuth-selenium-tellurium thin film material as claimed in claim 1, wherein the metal electrode is gold, silver, platinum or indium.

6. The bismuth-selenium-tellurium film material-based light and heat detector as claimed in claim 1, wherein the diameter d of the metal lead is 0< d <0.2 mm.

7. The method for preparing the optical and thermal detector based on the bismuth-selenium-tellurium film material as claimed in claim 1, which is characterized by comprising the following steps:

(a) placing the bismuth-selenium-tellurium target material and the cleaned and dried beveled oxide single crystal substrate in a deposition chamber of pulse laser deposition equipment for later use;

(b) bombarding the bismuth-selenium-tellurium target material by laser in pulse laser deposition equipment, and growing a bismuth-selenium-tellurium film on a beveled oxide single crystal substrate to obtain an edgecAn axis-tilted growth bismuth-selenium-tellurium film and a transverse thermoelectric element comprising the bismuth-selenium-tellurium film;

(c) preparing two symmetrical metal electrodes on the upper surface of the transverse thermoelectric element by adopting an evaporation plating, magnetron sputtering or pulse laser deposition method;

(d) and connecting a metal lead on the obtained metal electrode.

8. The method for preparing a light and heat detector based on a bismuth-selenium-tellurium film material as claimed in claim 7, wherein in the step (a), the bismuth-selenium-tellurium target material is prepared by a solid powder sintering method.

9. The method for preparing a photo-thermal detector based on a bismuth-selenium-tellurium thin film material as claimed in claim 7, wherein in the step (b), the deposition temperature of the pulsed laser deposition device is 250-350 ℃, and the oxygen partial pressure is 0.1-1 Pa.

10. The method for preparing a light and heat detector based on a bismuth-selenium-tellurium film material as claimed in claim 7, wherein in the step (b), the thickness of the bismuth-selenium-tellurium film is 30-150 nm.

Technical Field

The invention relates to a novel optical and thermal detector, in particular to an optical and thermal detector designed based on a transverse thermoelectric effect of a bismuth-selenium-tellurium film material and a preparation method thereof.

Background

The transverse thermoelectric effect is a thermoelectric effect in which the temperature difference and the voltage direction are perpendicular to each other. This particular thermoelectric effect arises from the anisotropy of the Seebeck coefficient of the material, which is generally only possible in the case of materials with a high degree of thermal stabilitycAxis-tilted growth thin films, single crystals, and artificially-built metal-metal or metal-semiconductor multilayer tilted structures. The light and heat detector designed and manufactured based on the transverse thermoelectric effect can realize the wide spectrum detection from ultraviolet to far infrared and various heat radiation detections, has the advantages of no need of refrigeration, no need of external power supply, capability of working in extreme environments such as high temperature and the like, and has important application prospects in various fields of military and national economy.

At present, the detector mostly selects multi-element oxide thin film materials such as a copper oxide high-temperature superconducting thin film, a manganese oxide giant magnetoresistance thin film, a layered cobalt oxide thermoelectric thin film and the like as detection elements, the preparation process is complex, the cost is higher, the output voltage sensitivity of the detector is lower, the time response is longer, and the commercial popularization is not facilitated.

Disclosure of Invention

One of the purposes of the invention is to provide a light and heat detector based on a bismuth-selenium-tellurium film material, so as to solve the problems of complex process, high cost and performance improvement of a transverse thermoelectric element made of the existing multi-element oxide film material.

The invention also aims to provide a preparation method of the light and heat detector based on the bismuth-selenium-tellurium film material, so as to prepare the light and heat detector with high detection sensitivity, quick response time and low cost.

One of the objects of the invention is achieved by:

a light and heat detector based on Bi-Se-Te film material comprises a transverse thermoelectric element, a metal electrode and a metal leadThe upper surface of the element is provided with two symmetrical metal electrodes, the metal electrodes are used for collecting voltage, and the metal lead is connected with the metal electrodes and used for transmitting voltage signals; the transverse thermoelectric element comprises a bismuth-selenium-tellurium filmcThe axis is grown obliquely on a chamfered oxide single crystal substrate.

The thickness of the bismuth-selenium-tellurium film is 30-150 nm, preferably 80-120 nm, and more preferably 100 nm; preferably, the bismuth-selenium-tellurium is Bi₂Se_xTe_3-x, 0＜x＜1。

The oxide single crystal substrate is in (001) orientation, the oblique cutting angle theta is more than 0 degree and less than 30 degrees, namely the bismuth-selenium-tellurium film is arranged alongcThe angle of the inclined growth of the shaft is more than 0 degree and less than 30 degrees. Optionally, the oxide single crystal substrate is lanthanum aluminate, strontium titanate, strontium tantalum lanthanum aluminate, magnesium oxide, sapphire or the like.

Alternatively, the metal electrode is gold, silver, platinum, indium, or the like.

Optionally, the diameter d of the metal lead is 0< d <0.2 mm.

The bismuth-selenium-tellurium film is grown on an oxide single crystal substrate by adopting a pulse laser deposition technology; the bismuth-selenium-tellurium target material can be prepared by adopting the existing method in the prior art, preferably a solid powder sintering method.

The light and heat detector based on the bismuth-selenium-tellurium film material can realize full spectrum detection from ultraviolet to infrared and can also realize various heat radiation detection. The wavelength of the radiation is 308 nm, and the irradiation energy is 0.25 mJ/mm²When the ultraviolet pulse laser irradiates the detector, the output voltage ranges from 5V to 11V respectively. Preferably, when the thickness of the bismuth-selenium-tellurium film is 100 nm, the output open-circuit voltage of the detector is 11V, and the response time is 100 ns; when the detector is irradiated by continuous light with the wavelength of 532 nm and the irradiation energy of 100 mW, the output voltage ranges are respectively 100-150 muV. Preferably, when the thickness of the bismuth-selenium-tellurium film is 100 nm, the amplitude of an open-circuit voltage signal output by the detector is 150 muV; when the detector is irradiated by near-infrared continuous light with the wavelength of 1064 nm and the laser energy of 100 mW, the output voltage ranges are 60-90 muV respectively. Preferably, when the bismuth-selenium-tellurium film isWhen the thickness is 100 nm, the amplitude of an open-circuit voltage signal output by the detector is 90 muV; when the detector is irradiated by near-infrared continuous light with the wavelength of 1550 nm and the laser energy of 100 mW, the output voltage ranges are respectively 30-45 muV. Preferably, when the thickness of the bismuth-selenium-tellurium film is 100 nm, the amplitude of an open-circuit voltage signal output by the detector is 45 muV; when the detector is heated, the output voltage ranges are 150-230 [ mu ] V respectively. Preferably, when the thickness of the bismuth-selenium-tellurium thin film is 100 nm, the output voltage amplitude is 230 μ V.

The second purpose of the invention is realized by the following steps:

a preparation method of a light and heat detector based on a bismuth-selenium-tellurium film material comprises the following steps:

(a) placing the bismuth-selenium-tellurium target material and the clean and dry oxide single crystal substrate in a deposition chamber of pulse laser deposition equipment for later use;

(b) bombarding the bismuth-selenium-tellurium target material by laser in pulse laser deposition equipment, and growing the bismuth-selenium-tellurium on a beveled oxide single crystal substrate to obtain an edgecAn axis-tilted growth bismuth-selenium-tellurium film and a transverse thermoelectric element comprising the bismuth-selenium-tellurium film;

(c) preparing two symmetrical metal electrodes on the upper surface of the transverse thermoelectric element;

(d) and connecting a metal lead on the obtained metal electrode.

In the step (a), preparing the bismuth-selenium-tellurium target material by adopting a solid powder sintering method; and cleaning the oxide single crystal substrate by adopting ultrasonic waves, and drying the oxide single crystal substrate in an inert atmosphere to obtain the clean and dry oxide single crystal substrate.

In the step (b), the deposition temperature of the pulsed laser deposition equipment is 250-350 ℃, and preferably 300 ℃; the oxygen partial pressure is 0.1-1 Pa; the laser energy is 1.2J/cm²The laser frequency was 5Hz, and the distance between the target and the substrate was 4 cm. The thickness of the bismuth-selenium-tellurium film is 30-150 nm, and preferably 80-120 nm; more preferably 100 nm; preferably, the bismuth-selenium-tellurium is Bi₂Se_xTe_3-xAnd x is more than 0 and less than 1. The oxide single crystal substrate is (001) oriented, and the beveling angle theta is more than 0 DEG and less than 30 deg. Bismuth-selenium-tellurium film edgecThe angle of the inclined growth of the shaft is more than 0 degree and less than 30 degrees. Optionally, the oxide single crystal substrate is lanthanum aluminate, strontium titanate, strontium tantalum lanthanum aluminate, magnesium oxide, sapphire or the like.

In the step (c), two symmetrical metal electrodes are prepared on the upper surface of the transverse thermoelectric element by adopting the technologies of evaporation plating, magnetron sputtering, pulsed laser deposition and the like. Alternatively, the metal electrode is gold, silver, platinum, indium, or the like.

In the step (d), the diameter d of the metal lead is 0< d <0.2 mm.

The invention adopts the pulse laser deposition technology to deposit bismuth, selenium and tellurium on a beveled oxide single crystal substrate to obtain an edgecThe bismuth-selenium-tellurium film grows in an axial inclination mode, and a light detector and a heat detector are manufactured by utilizing the transverse thermoelectric effect of the bismuth-selenium-tellurium film. The detector has the advantages of simple process, low cost, high detection sensitivity and quick response time, can realize detection of various thermal radiation, and has wide application prospect.

Drawings

FIG. 1 is the X-ray diffraction diagram of the bismuth-selenium-tellurium thin film material prepared in example 1.

Fig. 2 is a schematic structural view of the optical/thermal detector of the present invention.

Fig. 3 is a graph of output voltage-time response of the optical and thermal detector based on the bismuth-selenium-tellurium film obtained in example 2 by irradiation of 308 nm ultraviolet pulse laser.

Fig. 4 is a 532 nm visible continuous laser irradiation output voltage-time response curve of the photo-thermal detector based on the bismuth-selenium-tellurium film obtained in example 2.

Fig. 5 is a 1064 nm infrared continuous laser irradiation curve of the output voltage-time response curve of the photo-thermal detector based on the bismuth-selenium-tellurium film obtained in example 2.

FIG. 6 is the output voltage-time response curve of the photo-thermal detector based on the Bi-Se-Te film obtained in example 2 by 1550 nm near infrared continuous laser irradiation.

Fig. 7 is an output voltage-time response curve of the bismuth-selenium-tellurium film-based optical and thermal detector obtained in example 2 by thermal irradiation with an electric soldering iron.

Detailed Description

The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.

Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and reagents used in the examples are commercially available or prepared by methods well known to those of ordinary skill in the art. The invention adopts laser with different wavelengths to irradiate the surface of the transverse thermoelectric element and adopts an oscilloscope or a source meter to record voltage signals.