CN114709291B - Infrared spectrum detector based on GeSe two-dimensional nanomaterials and preparation method thereof - Google Patents

Abstract

The invention discloses an infrared spectrum detector based on GeSe two-dimensional nanomaterials and a preparation method thereof, which belongs to the field of infrared spectrum detector devices. The infrared spectrum detector includes a gate electrode formed by inkjet printing on a substrate, an insulating layer, and a source. Drain electrode, two-dimensional nanomaterial layer, and semiconductor active layer. The present invention can sense wide-spectrum infrared signals and convert optical signals into electrical signals. It combines machine learning methods to perform spectroscopic identification and processing of the spectrum, replacing traditional spectrum sensors. Gratings are used for light splitting. The two-dimensional nano-GeSe sheets used have strong photosensitivity in the infrared band, which improves the sensitivity of the spectral sensor. In addition, the sensor target surface composed of this material matches the readout circuit, and the device is highly integrated.

Description

Infrared spectrum detector based on GeSe two-dimensional nanomaterials and preparation method thereof

Technical field

The invention belongs to the field of infrared spectrum detector devices, and specifically relates to an intelligent sensing GeSe two-dimensional nano-infrared spectrum detector and a preparation method thereof.

technical background

Infrared spectrum detection plays a key role in important fields such as biomedicine, industrial testing, and military industry. In recent years, new nanometer-sized semiconductor materials represented by two-dimensional nanomaterials have outstanding advantages: high detection sensitivity, extremely low dark current, and the ability to work in high-temperature environments. These indicators have surpassed traditional thin film devices and are one of the strong competitors in the new generation of infrared detection technology. However, traditional two-dimensional nano-infrared detectors still have the following shortcomings in practical applications, including: 1. It requires complex and expensive integrated circuit processes to construct the detection target surface of the linear array; 2. It requires the use of expensive and fragile gratings for spectral analysis. The sensor splits light in advance; 3. The sensor target surface made of infrared materials does not match the silicon-based circuit, resulting in poor compatibility and low integration.

Two-dimensional nanomaterials represented by graphene have excellent optical and electrical properties, and the carrier mobility at room temperature can reach 10 ⁴ . However, graphene lacks an intrinsic band gap, which is not conducive to the construction of switches with high detection efficiency. Optoelectronic devices with large ratio and low power consumption. Other two-dimensional materials, such as molybdenum disulfide, have a wide band gap, but their carrier mobility is very low; black phosphorus has high carrier mobility and a suitable band gap, but black phosphorus is easily oxidized in the air . Compared with the above two-dimensional nanomaterials, GeSe is theoretically considered to be the only material with a direct band gap, and the spectral range of this material is predicted to cover almost the entire solar spectrum, with high carrier mobility and high stability. sex. These properties make GeSe the most promising candidate material in the field of infrared spectroscopy detection. At present, traditional infrared spectrum detectors usually use gratings for advance spectroscopy. Gratings are expensive and easily broken. Therefore, this project uses machine learning methods to replace spectroscopic spectroscopy and realize the reconstruction of optical signals in different bands. The purpose of reducing the production cost of the detector and improving the detection efficiency of the detector is achieved.

Contents of the invention

The purpose of the present invention is to design and develop an intelligent sensing GeSe two-dimensional nano-infrared spectrum detector to realize the detection of multi-band infrared spectrum. Overcome the inherent shortcomings of traditional sensors such as low detection accuracy, narrow detection band, and difficulty in converting optical signals to electrical signals; at the external end of the detector, machine learning is used to replace the spectroscopic grating for light splitting. The GeSe two-dimensional nanomaterial used is matched with the silicon-based circuit, and the detector is highly integrated, reducing the cost of the sensor. Another object of the present invention is to provide a method for preparing an intelligent sensing GeSe two-dimensional nano-infrared spectrum detector.

The technical solution adopted by the present invention is: an intelligent sensing GeSe two-dimensional nano-infrared spectrum detector, including a gate electrode, an insulating layer, a source and drain electrode, a two-dimensional nano material photosensitive layer, and a semiconductor active layer formed on a substrate. layer, in which the gate electrode is placed on the bottom layer, and from bottom to top are the insulating layer, source and drain electrodes, two-dimensional nanomaterial photosensitive layer, and semiconductor active layer. When the spectral detector is driven by a certain voltage, the GeSe two-dimensional nanomaterial photosensitive layer can convert the optical signal of the infrared light source into an electrical signal. The function of the semiconductor active layer is to increase the conductivity of the device.

The insulating layer can be a solid insulating layer such as silicon dioxide, silicon nitride, or aluminum oxide using chemical vapor deposition, atomic layer deposition, or magnetron sputtering, or it can be PMMA, Su8, or Su8 manufactured using spin coating, printing, or dispensing methods. Sol-gel organic gate insulating layer.

The two-dimensional nanomaterial photosensitive layer is composed of two-dimensional nanomaterial GeSe.

The thickness of the insulating layer is 100-120nm, the thickness of the two-dimensional nanomaterial photosensitive layer is 1-30nm, and the thickness of the semiconductor active layer is 60-80nm. A unique single-sided nanoheterojunction is constructed to improve the electrical performance of the device. Enhance the photosensitive efficiency of photodetectors.

The material used in the semiconductor active layer may be one of cadmium selenide, lead selenide, lead sulfide, lead oxide, etc.

Spectroscopy uses infrared spectrum current reconstruction instead of traditional grating spectroscopy, including three steps of learning, sampling and reconstruction. In the learning process, an n×n matrix is generated; in the sampling step, it is decomposed into a matrix equation through discretization; in the reconstruction By solving the matrix equation in the process, the spectrum of the incident light can be reconstructed.

The preparation method of the above-mentioned intelligent sensing GeSe two-dimensional nano-infrared spectrum detector includes the following steps:

1) Use inkjet printing on transparent glass to make the gate electrode of the sensor, and anneal at 150°C for 30 minutes;

2) Use spin coating, printing or dispensing methods to manufacture PMMA, Su8 and other sol-gel organic gate insulating layers, and cover them on the gate electrode;

3) After the electrodes are aligned, continue to use inkjet printing to manufacture the source and drain electrodes on the insulating layer, and also set a step temperature annealing on the temperature-adjusting hot stage for 30 minutes;

4) Use spin coating to evenly distribute the GeSe two-dimensional nanomaterials on the device. After repeating 2-3 times, the photosensitivity and absorption coefficient of the GeSe two-dimensional nanolayer can be improved, thereby improving the photoelectric conversion efficiency of the detector; 5) Finally Magnetron sputtering is used to cover the semiconductor material on the two-dimensional nanomaterial photosensitive layer, and the thickness of the semiconductor layer is controlled at 60-80nm.

Beneficial effects: The intelligent sensing GeSe two-dimensional nano-infrared spectrum detector of the present invention uses a self-designed sensor array target surface, replacing the complex and expensive integrated circuit process to construct a linear array detection target surface. At the same time, the use of GeSe as the two-dimensional nanomaterial used in the sensor not only improves the detection efficiency of the detector in the infrared band, but also solves the problem of mismatch between the sensor target surface composed of other infrared materials and the silicon-based circuit. Finally, in terms of light splitting, the present invention no longer uses the grating light splitting method used in traditional sensors. Instead, it uses machine learning to reconstruct optical signals in different bands, reducing the manufacturing cost of sensor devices. The device's turn-on voltage is 3.3v, the detection band is infrared, the detection efficiency is stable with voltage changes, the detection wavelength range is 650-860nm, the power consumption is as low as 1nw, and the detection efficiency EQE>700%.

Description of the drawings

Figure 1 is a schematic structural diagram of the GeSe two-dimensional nano-infrared spectrum detector for intelligent sensing;

Figure 2 is a TEM micrograph of the GeSe two-dimensional nanolayer/PbSe semiconductor heterojunction detection channel;

Figure 3 is a spectrum curve reconstructed by the intelligent sensing GeSe two-dimensional nano-infrared spectrum detector;

Figure 4 is the photoelectric conversion curve of the spectrum detector of the present invention;

Figure 5 is the photoelectric response characteristic curve of the spectrum detector of the present invention;

Reference signs: 1-gate electrode, 2-insulating layer, 3-source-drain electrode, 4-GeSe two-dimensional nanomaterial photosensitive layer, 5-semiconductor active layer.

Detailed ways:

The present invention will be further described below with reference to specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. After reading the present invention, those skilled in the art will be familiar with various equivalent forms of the present invention. All modifications fall within the scope defined by the appended claims of this application.

Example 1:

The intelligent sensing GeSe two-dimensional nano-infrared spectrum detector device, as shown in Figure 1, includes a gate electrode 1 formed on the substrate, an insulating layer 2, a source and drain electrode 3, and a GeSe two-dimensional nano material photosensitive layer 4. Semiconductor active layer 5, the gate electrode is placed on the bottom layer, and from bottom to top are the insulating layer, source and drain electrodes, GeSe two-dimensional nanomaterial photosensitive layer, and semiconductor active layer. The gate electrode and source and drain electrodes can be formed on the substrate through silver ion inkjet printing or laser etching; the insulating layer can be silicon dioxide, silicon nitride, aluminum oxide, etc. using chemical vapor deposition or atomic layer deposition. Or the solid insulating layer of magnetron sputtering, or the organic gate insulating layer of PMMA, Su8 and other sol-gels manufactured by spin coating, printing or dispensing methods; the photosensitive layer uses a new two-dimensional nanomaterial GeSe, which improves the The detection efficiency of the detector in infrared; the semiconductor active layer can be one of cadmium selenide, lead selenide, lead sulfide, lead oxide, etc., with the purpose of improving the conductivity of the device. The thickness of the insulating layer is 100nm, the thickness of the two-dimensional nanomaterial photosensitive layer is 60nm, the thickness of the semiconductor active layer is 10nm, and the turn-on voltage of the intelligent sensing GeSe two-dimensional nano-infrared spectrum detector device is 3.3v. ;Power consumption as low as 1nw; detection efficiency EQE>700%.

The preparation method of the above-mentioned intelligent sensing GeSe two-dimensional nano-infrared spectrum detector device includes the following steps:

1) Use inkjet printing on transparent glass to make the gate electrode of the sensor, and anneal at 150°C for 30 minutes;

2) Use spin coating, printing or dispensing methods to manufacture PMMA, Su8 and other sol-gel organic gate insulating layers, and cover them on the gate electrode;

3) After passing the calibration, continue to use inkjet printing to manufacture the source and drain electrodes on the insulating layer, and also set the step temperature annealing on the temperature-adjusting hot stage for 30 minutes;

4) Use spin coating to evenly distribute the GeSe two-dimensional nanomaterials on the device. After repeating 2-3 times, the photosensitivity and absorption coefficient of the GeSe two-dimensional nanolayer can be improved, thereby improving the photoelectric conversion efficiency of the detector; 5) Finally Magnetron sputtering is used to cover the semiconductor material on the two-dimensional nanomaterial photosensitive layer.

The turn-on voltage is 3.3v; the power consumption is as low as 1nw; the detection efficiency EQE>700%.

Example 2:

The intelligent sensing GeSe two-dimensional nano-infrared spectrum detector device, as shown in Figure 1, includes a gate electrode 1 formed on the substrate, an insulating layer 2, a source and drain electrode 3, and a GeSe two-dimensional nano material photosensitive layer 4. Semiconductor active layer 5, the gate electrode is placed on the bottom layer, and from bottom to top are the insulating layer, source and drain electrodes, GeSe two-dimensional nanomaterial photosensitive layer, and semiconductor active layer. The thickness of the insulating layer is 120nm, the thickness of the two-dimensional nanomaterial photosensitive layer is 80nm, and the thickness of the semiconductor active layer is 20nm. The turn-on voltage of the intelligent sensing GeSe two-dimensional nano-infrared spectrum detector device is 3.3v. ;Power consumption as low as 1nw; detection efficiency EQE>700%.

The preparation method of the above-mentioned intelligent sensing GeSe two-dimensional nano-infrared spectrum detector device includes the following steps:

1) Use inkjet printing on transparent glass to make the gate electrode of the sensor, and anneal at 150°C for 30 minutes;

2) Use spin coating, printing or dispensing methods to manufacture PMMA, Su8 and other sol-gel organic gate insulating layers, and cover them on the gate electrode;

3) After passing the calibration, continue to use inkjet printing to manufacture the source and drain electrodes on the insulating layer, and also set the step temperature annealing on the temperature-adjusting hot stage for 30 minutes;

4) Use spin coating to evenly distribute the GeSe two-dimensional nanomaterials on the device. After repeating 2-3 times, the photosensitivity and absorption coefficient of the GeSe two-dimensional nanolayer can be improved, and thus the detector's performance can be improved. Photoelectric conversion efficiency;

5) Finally, magnetron sputtering is used to cover the semiconductor material on the two-dimensional nanomaterial photosensitive layer.

The turn-on voltage is 3.3v; the power consumption is as low as 1nw; the detection efficiency EQE>700%.

Furthermore, the intelligent sensing GeSe two-dimensional nano-infrared spectrum detector device uses the infrared spectrum current reconstruction method instead of the traditional spectrum detector using gratings for spectrometry. Its working plan includes three steps: learning, sampling and reconstruction.

The optical properties of GeSe can be tuned by an external bias displacement field (D), which is controlled by the voltage applied to the gate electrode. The optical responsivity (R) can be formed as a function and matrix by the incident light wavelength (λ) and the external bias displacement field D.

During the learning process, the continuous response function R(D,λ) can be discretized into a matrix R _D,λ . Response row vector in R _D,λ This can be done by measuring the optical response of multiple known incident spectra at each electric displacement field _Di. After completing the learning process of all n displacement fields, a complete n×n matrix can be generated.

In the sampling step, the photocurrent response of the incident light to the unknown spectrum is measured under n different displacement fields (D ₁ ~D _n ), and the response vector _ID is obtained. And since the photocurrent (I) depends on the blackbody light source temperature T and the spectral responsivity R (λ), at a given displacement D _i , the photocurrent I (T) is the ratio of the incident spectral power density to the entire wavelength of λ ₁ to λ _n The integral of the product of response rates, Where T=T ₁ , T ₂ ,...T _n , the incident power density P (T, λ) depends on the wavelength λ and the temperature T, which can be calculated according to Planck's law. When the temperature is from T1 to Tn, n integral equations can be obtained, which are decomposed into a matrix equation through discretization as follows (1), abbreviated as R×P _T,λ =I _T .

During the reconstruction process, the response vector ID measured in the sampling step is brought into the R× _PT,λ = _IT matrix equation ( _PT,λ has been derived from Planck’s law), and the R matrix can be solved, The spectrum of the incident light can be reconstructed by comparing the response matrix R(D,λ) generated by the learning process.

In the description of this specification, reference to the terms "one embodiment," "example," "specific example," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one aspect of the invention. in an embodiment or example. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the industry should understand that the present invention is not limited by the above embodiments. The above embodiments and descriptions only illustrate the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will also have other aspects. Various changes and modifications are possible, which fall within the scope of the claimed invention.

Claims (6)

1. An intelligent sensing GeSe two-dimensional nanometer infrared spectrum detector is characterized in that; the detector substrate is provided with a GeSe two-dimensional nano material photosensitive layer (4), the GeSe two-dimensional nano material photosensitive layer (4) can be prepared by a large-area spin coating process, and a plurality of layers of GeSe two-dimensional nano materials can be continuously coated on the surface of the photosensitive layer to enhance the photoelectric absorption efficiency;

the substrate is sequentially provided with a gate electrode (1), a gate insulating layer (2), a source-drain electrode (3), a GeSe two-dimensional nano material photosensitive layer (4) and a semiconductor active layer (5), wherein the gate electrode is arranged on the bottom layer, the gate insulating layer (2), the source-drain electrode (3), the GeSe two-dimensional nano material photosensitive layer (4) and the semiconductor active layer (5) are sequentially arranged from bottom to top, and the gate electrode (1) is formed by ink-jet printing;

the material of the gate insulating layer (2) is one of silicon dioxide, silicon nitride and aluminum oxide;

the semiconductor active layer (5) is made of one of cadmium selenide, lead sulfide and lead oxide.

2. The intelligent sensing GeSe two-dimensional nano infrared spectrum detector according to claim 1, wherein the detector comprises; the gate insulating layer (2) is formed by chemical vapor deposition, atomic layer deposition or magnetron sputtering processing.

3. The intelligent sensing GeSe two-dimensional nano infrared spectrum detector according to claim 1, wherein: the gate insulating layer (2) is an organic gate insulating layer of PMMA or Su8 sol-gel manufactured by a spin coating, printing or dispensing method.

4. The intelligent sensing GeSe two-dimensional nano infrared spectrum detector, according to claim 1, uses the grid electrode (1) to regulate and control a photosensitive layer/a semiconductor active layer, and the spectrum detector performs light splitting through infrared spectrum current responses and an incident light reconstruction method of different wave bands l, wherein the method comprises three steps of machine learning of the spectrum current responses of different lambda, sampling of characteristic response signals of measured light and reconstruction of the spectrum responses of the measured light.

5. The intelligent sensing GeSe two-dimensional nano infrared spectrum detector according to any one of claims 1-3, wherein the infrared spectrum detector processing comprises the steps of:

1) Manufacturing a gate electrode of the sensor on transparent glass using inkjet printing, and annealing at a temperature of 150 ℃ for 30 minutes;

2) Manufacturing PMMA and Su8 sol-gel organic gate insulating layers by using spin coating, printing or dispensing, and covering the organic gate insulating layers on the gate electrode;

3) Continuously manufacturing a source electrode and a drain electrode by using ink-jet printing on the insulating layer, and setting a step temperature through a temperature-adjusting heat table for annealing for 30 minutes;

4) The GeSe two-dimensional nano material is uniformly distributed on the device by utilizing spin coating, and the photosensitive efficiency of the GeSe two-dimensional nano layer can be improved after repeating for 2-3 times;

5) And finally, covering the semiconductor material on the two-dimensional nano material photosensitive layer by utilizing magnetron sputtering, wherein the thickness of the semiconductor layer is controlled to be 60-80nm.

6. The intelligent sensing GeSe two-dimensional nano infrared spectrum detector is characterized in that a grid electrode (1), a grid insulating layer (2), a source-drain electrode (3), a GeSe two-dimensional nano material photosensitive layer (4) and a semiconductor active layer (5) are sequentially arranged on a substrate, the grid electrode is arranged on a bottom layer, the grid insulating layer (2), the source-drain electrode (3), the GeSe two-dimensional nano material photosensitive layer (4) and the semiconductor active layer (5) are sequentially arranged from bottom to top, and the grid electrode (1) is formed by ink-jet printing.