阅读说明：本技术 一种PtSx高性能光电器件及其制备方法和应用 (PtSxHigh-performance photoelectric device and preparation method and application thereof ) 是由 张宇 韩琳 张云红 王彦皓 于 2021-09-09 设计创作，主要内容包括：本发明涉及一种PtS-(x)高性能光电器件及其制备方法和应用,包括由下自上依次生长的基底、PtS-(x)薄层、两个电极,所述基底的上表面生长有所述PtS-(x)薄层,所述PtS-(x)薄层的上表面设有所述两个电极,1≤x≤2,PtSx薄层通过化学气相沉积法,利用硫化氢气体、氢气和氩气的混合气体,在高温条件下硫化图形化金属铂薄层获得。光电器件通过图形化金属硫化和电极沉积工艺制备,可大面积制备PtS-(x)薄膜和光电器件。本发明所公开的光电器件具有宽光电响应窗口,光电性能高,稳定好,检测灵敏度高,超高的外量子效率,制作简单,成本低,在光电子器件、气体传感器和电子器件领域具有极大的应用潜力。(The invention relates to a PtS x A high-performance photoelectric device comprises a substrate and PtS sequentially grown from bottom to top x A thin layer, two electrodes, the PtS grown on the upper surface of the substrate x Thin layer of said PtS x The upper surface of the thin layer is provided with the two electrodes, x is more than or equal to 1 and less than or equal to 2, and the PtSx thin layer is communicated withAnd (3) carrying out chemical vapor deposition, and vulcanizing the patterned metal platinum thin layer under a high-temperature condition by using a mixed gas of hydrogen sulfide gas, hydrogen and argon. The photoelectric device is prepared by the graphical metal vulcanization and electrode deposition process, and the PtS can be prepared in large area x Thin films and optoelectronic devices. The photoelectric device disclosed by the invention has a wide photoelectric response window, high photoelectric performance, good stability, high detection sensitivity, ultrahigh external quantum efficiency, simple manufacture and low cost, and has great application potential in the fields of photoelectric devices, gas sensors and electronic devices.)

1. PtS_xA high-performance photoelectric device, comprising a substrate, PtS, grown in this order from bottom to top_xA thin layer, two electrodes, the PtS grown on the upper surface of the substrate_xThin layer of said PtS_xThe upper surface of the thin layer is provided with the two electrodes, and x is more than or equal to 1 and less than or equal to 2.

2. A PtS according to claim 1_xHigh performance optoelectronic devices, wherein said PtS_xThe material of the thin layer is PtS₂And PtS.

3. A PtS according to claim 1_xHigh performance optoelectronic devices, wherein said PtS_xThe thickness of the thin layer is 1-30 nm;

further preferably, the PtS_xThe thickness of the thin layer is 3-11 nm;

most preferably, the PtS_xThe thickness of the thin layer was 11 nm.

4. According toA PtS according to claim 1_xThe high-performance photoelectric device is characterized in that the spectral response range of the photoelectric device is 200-1500 nm; the substrate is sapphire, gallium nitride or silicon carbide.

5. A PtS according to claim 1_xThe high-performance photoelectric device is characterized in that the two electrodes comprise a first electrode and a second electrode, the first electrode is any one of a Ti/Au combined electrode, a Ti/Al/Ni/Au combined electrode and a Ti/Al/Pt/Au combined electrode, and the second electrode is any one of the Ti/Au combined electrode, the Ti/Al/Ni/Au combined electrode and the Ti/Al/Pt/Au combined electrode.

6. PtS according to any one of claims 1 to 5_xThe preparation method of the high-performance photoelectric device is characterized by comprising the following steps of:

(1) and (3) Pt deposition: depositing a graphical metal platinum thin layer on the surface of a substrate;

(2) and (3) vulcanization: vulcanizing the patterned metal platinum thin layer by using a mixed gas of hydrogen sulfide gas, hydrogen and argon through a chemical vapor deposition method under a high-temperature condition, wherein the high-temperature condition is not lower than 150 ℃;

(3) and (3) natural cooling: naturally cooling to form PtS_xA thin layer;

(4) and (3) electrode deposition: designing the pattern of two electrodes and the length of a channel through a mask, and patterning PtS in each pattern in an electron beam evaporation mode_xPreparing two electrodes on the thin layer to form PtS_xHigh performance optoelectronic devices.

7. The PtS of claim 6_xThe preparation method of the high-performance photoelectric device is characterized in that in the step (2), the patterned metal platinum thin layer is vulcanized at the temperature of 400-700 ℃;

most preferably, the patterned platinum metal layer is sulfided in step (2) at 700 ℃.

8. The PtS of claim 6_xThe preparation method of the high-performance photoelectric device is characterized in that in the step (2), in the mixed gas of hydrogen sulfide gas, hydrogen gas and argon gas, the hydrogen sulfide gas is 60sccm, the hydrogen gas is 20sccm, and the argon gas is 60 sccm; the vulcanizing time is 30-180 min.

9. The PtS of claim 6_xThe preparation method of the high-performance photoelectric device is characterized in that in the step (1), a graphical metal platinum thin layer graph is designed through a mask, and 1-10nm metal platinum is deposited on a substrate in an electron beam evaporation mode to form a graphical metal platinum thin layer;

further preferably, 1-5nm of platinum metal is deposited on the substrate by means of electron beam evaporation.

10. PtS according to any one of claims 1 to 5_xUse of a high performance opto-electronic device, characterized in that PtS between a first electrode and a second electrode is applied_xThe thin layer is set as an illumination area for performing light detection or used as a gas detector.

Technical Field

The invention relates to a photoelectric device, in particular to a PtS_xHigh-performance photoelectric device and its preparation method and application.

Background

Platinum sulfide thin film materials and devices have been receiving attention from researchers as one of the two-dimensional materials and devices emerging in recent years. The forbidden band width can be adjusted according to the thickness, the wide spectrum response, the ultra-sensitive gas response and the ultra-stable material property in the air, so the material has a far-reaching application prospect in the fields of photoelectric devices, gas detection and electronic information, and the growth process is simpler and has higher stability, thereby the material is widely concerned. Currently, high quality platinum sulfide crystals are limited by their crystal size and price, greatly limiting their rapid progress in development and application.

In order to rapidly promote the rapid development and application of platinum sulfide materials and devices, researchers mostly adopt sulfur vapor formed by evaporating sulfur powder to vulcanize metal platinum to form a platinum disulfide film or a platinum sulfide film, but the quality and the efficiency of the platinum sulfide film prepared by the method are poor, and the performance of the prepared platinum sulfide materials and devices is poor, so that the application of the platinum sulfide materials and devices is greatly influenced. Therefore, the development of a platinum sulfide photoelectric device which has high performance, high stability, low cost and large-area preparation has great significance in the fields of aerospace, oceans and civil use.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a PtS_xThe invention relates to a high-performance photoelectric device and a preparation method thereof, wherein a platinum sulfide material and a device are prepared by using mixed gas of hydrogen sulfide, hydrogen and argon to replace sulfur powder, so that the performance of a platinum sulfide film and the device is improved, and the preparation efficiency of the platinum sulfide film material and the device is improved. Large-area preparation is achieved, the cost is low, and the manufacture is simpleAnd has the purposes of wide response spectrum, improved photoelectric response and super stability.

The invention also provides the PtS_xApplication of high-performance photoelectric devices.

Interpretation of terms:

1. chemical vapor deposition, a process for the preparation of one or more novel substances by reaction of a gas and a gas, or a gas and a solid, in a chamber under specific conditions

2. Sulfurizing, i.e. the process of generating new sulfide by reacting sulfur-containing gas with other substances.

In order to achieve the purpose, the technical scheme of the invention is as follows:

PtS_xHigh-performance photoelectric device comprising a substrate, PtS, grown in succession from bottom to top_xA thin layer, two electrodes, the PtS grown on the upper surface of the substrate_xThin layer of said PtS_xThe upper surface of the thin layer is provided with the two electrodes, and x is more than or equal to 1 and less than or equal to 2.

According to the invention, preferably, the PtS_xThe material of the thin layer is PtS₂And PtS.

According to the invention, preferably, the PtS_xThe thickness of the thin layer is 1-30 nm;

further preferably, the PtS_xThe thickness of the thin layer is 3-11 nm;

most preferably, the PtS_xThe thickness of the thin layer was 11 nm.

Preferably, according to the invention, the spectral response range of the photoelectric device is 200-1500 nm.

Preferably according to the invention, the substrate is sapphire or gallium nitride or silicon carbide.

According to the present invention, it is preferable that the two electrodes include a first electrode which is any one of a Ti/Au combined electrode, a Ti/Al/Ni/Au combined electrode, and a Ti/Al/Pt/Au combined electrode, and a second electrode which is any one of a Ti/Au combined electrode, a Ti/Al/Ni/Au combined electrode, and a Ti/Al/Pt/Au combined electrode.

PtS described above_xMethod for preparing high-performance photoelectric deviceThe method comprises the following steps:

(1) and (3) Pt deposition: depositing a graphical metal platinum thin layer on the surface of a substrate;

(2) and (3) vulcanization: vulcanizing the patterned metal platinum thin layer by using a mixed gas of hydrogen sulfide gas, hydrogen and argon through a chemical vapor deposition method under a high-temperature condition, wherein the high-temperature condition is not lower than 150 ℃;

(3) and (3) natural cooling: naturally cooling to form PtS_xA thin layer;

(4) and (3) electrode deposition: designing the pattern of two electrodes and the length of a channel through a mask, and patterning PtS in each pattern in an electron beam evaporation mode_xPreparing two electrodes on the thin layer to form PtS_xHigh performance optoelectronic devices.

Preferably, in step (2), the hydrogen sulfide gas, the hydrogen gas and the argon gas are mixed at a flow rate of 60sccm, 20sccm and 60sccm, respectively.

Preferably, in step (2), the patterned platinum metal thin layer is vulcanized at 400-700 ℃.

Most preferably, the patterned platinum metal layer is sulfided in step (2) at 700 ℃.

Preferably, according to the invention, in step (2), the vulcanization time is from 30 to 180 min.

Preferably, in the step (1), a patterned metal platinum thin layer pattern is designed through a mask, and 1-10nm metal platinum is deposited on the substrate in an electron beam evaporation mode to form a patterned metal platinum thin layer;

further preferably, 1-5nm of platinum metal is deposited on the substrate by means of electron beam evaporation.

According to the invention, after the sapphire is ultrasonically cleaned in acetone for 10 minutes, the substrate is obtained by alternately cleaning the sapphire with ethanol and deionized water for 3 times.

Preferably, in step (4), the two electrodes are Ti/Au electrodes or Cr/Au electrodes formed by electron beam evaporation.

PtS described above_xApplication of high-performance photoelectric devicePtS between one electrode and a second electrode_xThe thin layer is set as an illumination area for performing light detection or used as a gas detector.

The invention has the beneficial effects that:

(1) the invention adopts the graphical design during the growth of the material, thereby realizing the large-area manufacture of the photoelectric device with simple process;

(2) the invention utilizes the excellent photoelectronic characteristics of the platinum disulfide and platinum sulfide mixed thin layer, and the prepared photoelectric device has high responsivity (0.31A/W), wide spectral responsivity (from ultraviolet to infrared), and low optical detectivity (9.17x 10)⁹Jones), ultrastable characteristics (a reduction of only 26% in the photoelectric response stored in air a year);

(3) PtS of the invention_xThe thin layer is formed by sulfurizing and evaporating a thin layer of metal platinum (PtS) on the surface of the substrate at high temperature with a mixture of hydrogen sulfide gas, hydrogen gas and argon gas_xThe film has PtS₂And PtS, and PtS_xFormed in one growth. Thereby improving the performance of materials and devices;

(4) PtS of the present invention_xThe high-performance photoelectric device has the advantages of low cost, high performance, simple manufacturing process and wide detection spectrum range, and has great application potential in the fields of photoelectric devices, gas detection, electronic information and the like.

Drawings

FIG. 1 shows a PtS of the present invention_xA high performance optoelectronic device schematic;

FIG. 2 shows a PtS of the present invention_xThe preparation flow schematic diagram of the high-performance photoelectric device;

FIG. 3 is a PtS representation of a photovoltaic device of the present invention_xA material characteristic analysis result graph;

FIG. 4 shows different PtS under the same optical power irradiation of the optoelectronic device of the present invention_xPhotocurrent contrast plot under thickness;

FIG. 5a is a graph showing the comparison of photocurrent at different optical power levels for a photovoltaic device of the present invention;

FIG. 5b is a graph of photocurrent versus voltage for an optoelectronic device of the present invention at different voltages;

FIG. 6 is a graph of photocurrent levels at different wavelengths for an optoelectronic device of the present invention;

FIG. 7 is a graph comparing the change curves of detectivity (D), responsivity (R) and External Quantum Efficiency (EQE) of the optoelectronic device of the present invention and other optoelectronic devices at different optical powers;

FIG. 8 is a graph comparing long term stability of photovoltaic devices of the present invention.

Wherein, 1, a substrate; 2. PtS_xA thin layer; 3. a first electrode; 4. a second electrode.

Detailed Description

The invention is further defined in the following, but not limited to, the figures and examples in the description.

Example 1

PtS_xA high performance photovoltaic device, as shown in FIG. 1, comprises a substrate 1, PtS, grown sequentially from bottom to top_xThin layer 2, two electrodes, substrate 1 with PtS grown on its upper surface_xThin layer 2, PtS_xThe upper surface of the thin layer 2 is provided with two electrodes, and x is more than or equal to 1 and less than or equal to 2.

PtS_xThe material of the thin layer 2 is PtS₂And PtS. Once growth is formed.

PtS_xThe thickness of the thin layer 2 is 1-30 nm;

the spectral response range of the photoelectric device is 200-1500 nm.

The substrate 1 is sapphire or gallium nitride or silicon carbide.

The two electrodes comprise a first electrode 3 and a second electrode 4, the first electrode 3 is any one of a Ti/Au combined electrode, a Ti/Al/Ni/Au combined electrode and a Ti/Al/Pt/Au combined electrode, and the second electrode 4 is any one of a Ti/Au combined electrode, a Ti/Al/Ni/Au combined electrode and a Ti/Al/Pt/Au combined electrode. The two electrodes have the same function and can be interchanged.

Example 2

A PtS as in embodiment 1_xHigh performance optoelectronic devices, distinguished by:

PtS_xthe thickness of the thin layer 2 is 3-11 nm; the substrate 1 is sapphire.

Example 3

A PtS as in embodiment 1_xHigh performance optoelectronic devices, distinguished by:

PtS_xthe thickness of the thin layer 2 is 11 nm.

PtS with thickness of 11nm_xUnder the condition of the thin layer 2, the photoelectric performance of the photoelectric device is greatly improved, and the photoelectric device has wide spectral responsivity (from ultraviolet to infrared range) and low optical detectivity (9.17x 10)⁹Jones) and ultrastable characteristics (a reduction of only 26% in the photoelectric response stored in air for one year) are superior in performance in platinum sulfide optoelectronic devices.

Example 4

PtS according to any one of embodiments 1 to 3_xThe preparation method of the high-performance photoelectric device, as shown in fig. 2, comprises the following steps:

(1) and (3) Pt deposition: designing a graphical metal platinum thin layer graph through a mask, and depositing 1-10nm metal platinum on the substrate 1 in an electron beam evaporation mode to form a graphical metal platinum thin layer; the c-surface sapphire is ultrasonically cleaned in acetone for 10 minutes, and then is alternately cleaned for 3 times by using ethanol and deionized water, so that a substrate 1 is obtained.

(2) And (3) vulcanization: by the chemical vapor deposition method, a hydrogen sulfide gas of 60sccm, a hydrogen gas of 20sccm, and an argon gas of 60sccm were used as a mixed gas. Vulcanizing the patterned metal platinum thin layer at the temperature of 400-700 ℃; the vulcanizing time is 30-180 min.

(3) And (3) natural cooling: naturally cooling to form PtS_xA thin layer 2;

(4) and (3) electrode deposition: designing the style and size of two electrodes through a mask plate, and patterning PtS in each pattern in an electron beam evaporation mode_xTwo electrodes are prepared on the thin layer 2 to form PtS_xHigh performance optoelectronic devices. The two electrodes are Ti/Au electrodes or Cr/Au electrodes formed by electron beam evaporation.

PtS obtained in example_xThe high performance optoelectronic device was subjected to performance testing, the circuit connection is as shown in fig. 1, V represents the voltage between the first electrode 3 and the second electrode 4, and the results were analyzed as follows:

according to the inventionPtS of photoelectric device_xThe material characteristic analysis is shown in fig. 3, the energy level energy of the electron outside the element core is shown on the abscissa, and the intensity of the energy is shown on the ordinate, so that the content of different energy levels of the element can be analyzed. As can be seen from FIG. 3, PtS was prepared_xLayer 2 is a compositional analysis of a composite of platinum monosulfide and platinum disulfide.

The photoelectric device of the invention has different PtS under the irradiation of the same optical power_xThe photocurrent versus thickness ratio is shown in fig. 4, with the abscissa referring to time and the ordinate referring to photocurrent. Following PtS_xThe increase of the thickness of the thin layer 2 increases the photoresponse intensity of the optoelectronic device under the irradiation of the same optical power.

Fig. 5a shows a graph of photocurrent contrast of the optoelectronic device under different light intensity irradiation, and fig. 5b shows a graph of photocurrent contrast of the optoelectronic device under different applied voltages V, which can be seen from the above two graphs: when V is 5V, a more obvious photocurrent can be obtained under different light intensities, and the photocurrent increases with the increase of the light intensity; similarly, under the condition of fixed light intensity, a more obvious photocurrent can be obtained under the condition that V is greater than 0, and the photocurrent is increased with the increase of the applied voltage.

As shown in FIG. 6, the photoelectric device has good photoelectric response at wavelengths of 405nm, 532nm and 660 nm.

Fig. 7 shows the change curves of detectivity (D), responsivity (R) and External Quantum Efficiency (EQE) of the optoelectronic device at different optical powers, and a comparison of the optoelectronic device fabricated on other substrates, from which it can be seen that both D and R, EQE increase with decreasing illumination intensity.

PtS prepared as shown in FIG. 8_xThe photoelectric device, in the case of packaging, still has 74% of original performance of photoelectric response performance after being stored in air for 1 year.

Example 5

PtS according to embodiment 4_xThe preparation method of the high-performance photoelectric device is characterized by comprising the following steps: depositing 1-5nm of metal platinum on the substrate 1 by means of electron beam evaporation.

In the step (2), the patterned metal platinum thin layer is vulcanized at 700 ℃.

Example 6

PtS according to any one of embodiments 1 to 5_xApplication of high-performance photoelectric device, PtS between first electrode 3 and second electrode 4_xThe thin layer 2 is set to be an illumination region for performing light detection or used as a gas detector.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.