Novel two-dimensional layered rare earth semiconductor material and preparation method and application thereof
Through chemical gas phase transfer method and two-stage sintering treatment, large-size and high-quality two-dimensional rare earth compounds were successfully prepared, solving the problem of fewer reports of two-dimensional layered rare earth materials in the existing technology, achieving excellent luminescence and photoelectric properties of the material, and expanding its application prospects in multiple fields.
Patent Information
- Application Number
- CN202510260397.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-06
- Publication Date
- 2025-06-06
AI Technical Summary
There are few reports on two-dimensional layered rare earth materials in the prior art, and the lack of new two-dimensional layered rare earth semiconductor materials limits their application in electronics, optoelectronics, energy and other fields.
Using chemical gas phase transport method, through two-stage sintering treatment, large-size and high-quality two-dimensional rare earth compounds were prepared, such as YSiTe3, HoSiTe3, LuSiTe3, and TmSiTe3. The method includes a first sintering stage melting the gas compound at the reaction end, and a second sintering stage performing physical vapor deposition under a temperature gradient driven.
The prepared two-dimensional layered rare earth material has excellent luminescence performance and photoelectric response, and is suitable for the field of luminescence and photoelectric detection. It has low process cost, simple operation, and meets environmental protection requirements.
Smart Images
Figure CN120097286A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of two-dimensional semiconductor materials, and specifically relates to a novel two-dimensional layered rare earth semiconductor material and a preparation method and application thereof. Background Art
[0002] Since Novoselov and Geim successfully produced a single-layer graphene for the first time in 2004, research on two-dimensional (2D) materials has flourished, and two-dimensional layered materials have been applied in many fields such as electronics, optoelectronics, and energy catalysis. So far, a large number of two-dimensional layered materials have been reported, among which the most representative two-dimensional materials are graphene, transition metal sulfides, hexagonal boron nitride, MXenes, transition metal carbides, black phosphorus, etc. These materials have excellent mechanical, electrical, optical and other properties, and show unprecedented performance under quantum confinement effects. They are suitable for optoelectronic devices, spintronic devices and other fields, and have attracted extensive attention and research from the scientific and industrial communities.
[0003] Rare earth elements include 17 metal elements, namely 15 lanthanide elements (La-Lu) and Sc and Y of group IIIB. Since their unfilled 4f orbitals are shielded by fully filled outer shells, the unpaired 4f electrons of rare earth ions usually do not participate in chemical reactions, thus having good properties in luminescence, magnetism, electronics and catalytic activities. For example, the unique f-d and f-f transitions of rare earth ions give them atomic-like optical properties, making rare earth ions have sharp absorption and fluorescence peaks. Based on this, rare earths have been widely used in light-emitting diodes (LEDs), lasers and bioimaging. At the same time, rare earth materials have great potential in spin electronics research due to their special electronic structure and magnetic behavior. The ultra-thin structure of 2D materials can cause novel physical phenomena such as electronic structure, ultra-large specific surface, quantum effect, etc. that are different from those of bulk materials, making them have very attractive application prospects in the new generation of electronics, optoelectronics and flexible devices. Therefore, more and more researchers are introducing rare earth ions into 2D materials in order to achieve a strong combination and collide with new sparks. However, there are few reports on two-dimensional layered rare earth materials, mainly focusing on rare earth oxyhalides (such as ErOCl) and rare earth sulfur halides (such as ScSI). Therefore, it is of great significance to explore and develop new two-dimensional layered rare earth materials. Because the new two-dimensional layered rare earth semiconductor materials of rare earth materials combine the unique properties of two-dimensional materials and rare earth elements, as a rising star in the two-dimensional field, they have great application potential and prospects in electronics, optoelectronics, energy, environment, biomedicine and other fields. Summary of the invention
[0004] In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a novel two-dimensional layered rare earth semiconductor material and its preparation method and application, and demonstrates the optical properties and photoelectric detection performance of the material. Moreover, the present invention has the advantages of low cost, simple synthesis method, and simple material preparation.
[0005] In order to achieve the above object, the technical solution adopted by the present invention is:
[0006] The first aspect of the present invention provides a novel two-dimensional layered rare earth semiconductor material, wherein the two-dimensional layered rare earth material comprises YSiTe 3 、HoSiTe 3 、LuSiTe 3 、TmSiTe 3 .
[0007] Preferably, the lateral dimension of the two-dimensional layered rare earth material exceeds 5 mm.
[0008] The second aspect of the present invention provides a method for preparing the new two-dimensional layered rare earth semiconductor material described in the first aspect, specifically: placing the growth raw materials rare earth metal RE (RE = Y, Ho, Lu, Tm), Si, Te powder and transfer agent in a quartz tube, sealing the quartz tube after vacuuming, and then placing it in a double-temperature zone tubular furnace for two-stage sintering treatment. In the first sintering stage, the raw materials are first melted at the reaction end and form gaseous compounds. In the second sintering stage, the temperature of the generation end is changed. Under the action of the temperature gradient driving force, the gaseous compounds are transferred from the reaction end (hot end) to the generation end (cold end), and physical vapor deposition is completed in this stage. After the end, the temperature is naturally lowered to obtain the two-dimensional layered rare earth material.
[0009] The present invention adopts the chemical vapor transport method to melt rare earth metals (RE=Y, Ho, Lu, Tm), Si, Te raw materials and a transport agent at the reaction end through a first sintering stage to form gaseous compounds; then the temperature of the generation section is changed, and under the action of the temperature gradient driving force, the gaseous compounds are transported from the hot end (reaction section) to the cold end (growth section), and then physical vapor deposition is carried out at the generation end of the quartz tube in the second sintering stage, and finally large-sized, high-quality two-dimensional rare earth compounds are grown.
[0010] Preferably, the total mass of the growth raw materials RE:Si:Te is 1-2 g, and the molar ratio is 1:1:3.
[0011] Preferably, the mass ratio of the total amount of growth raw materials to the amount of transfer agent is 20:1; the transfer agent is I 2 .
[0012] Preferably, the temperature of the first sintering stage is 900° C. at the reaction end, with a heating rate of 5° C. / min; 1000° C. at the generation end, with a heating rate of 10° C. / min; and the temperature is kept for 6 hours.
[0013] Preferably, the temperature of the second sintering stage is 900° C. at the reaction end and 850° C. at the production end, and the cooling rate at the production end is 10° C. / min; the temperature is kept for 168 hours.
[0014] The third aspect of the present invention provides the use of the novel two-dimensional layered rare earth semiconductor material described in the first aspect in light-emitting devices and / or photoelectric detection devices.
[0015] The large-sized, high-quality two-dimensional rare earth compound prepared by the method of the present invention has excellent luminescence performance and photoelectric response, and can be applied to the fields of luminescence and photoelectric detection.
[0016] Preferably, the novel two-dimensional layered rare earth semiconductor material described in the first aspect is firstly peeled off into a few-layer two-dimensional material by mechanical peeling method, and then transferred to a silicon wafer by PDMS, and then a conductive electrode is prepared on the surface of the silicon wafer material by photolithography and electron beam evaporation process, so as to obtain a photoelectric detection device.
[0017] More preferably, the thickness of the few-layer two-dimensional material is less than 100 nm, and the conductive electrode is composed of 10 nm Ti and 70 nm Au.
[0018] More preferably, the surface layer of the silicon wafer is silicon dioxide, silicon dioxide (SiO 2 ) thickness is 285nm.
[0019] Compared with the prior art, the present invention has the following beneficial effects:
[0020] The present invention selects rare earth metals (RE = Y, Ho, Lu, Tm, etc.), Si, and Te as raw materials, adopts chemical vapor transport method under the joint action of two sintering mechanisms to prepare large-sized, high-quality two-dimensional rare earth compounds (including YSiTe 3 、HoSiTe 3 、LuSiTe 3 、TmSiTe 3 The obtained two-dimensional layered rare earth material has excellent luminescence performance and photoelectric response, and is expected to be applied in the field of luminescence and photoelectric detection. Specifically, the present invention has the following advantages:
[0021] (1) The present invention provides a two-dimensional layered rare earth material, which uses rare earth metals (RE = Y, Ho, Lu, Tm), Si, and Te as raw materials, and successfully prepares large-sized, high-quality two-dimensional rare earth compounds (including YSiTe) by chemical vapor transport for the first time. 3 、HoSiTe 3 、LuSiTe 3 、TmSiTe 3etc.), and the above materials are synthesized for the first time, which enriches the large family of two-dimensional layered rare earth materials and provides new choices and platforms for exploring the mechanical, electrical, optical and photoelectric properties of two-dimensional layered rare earth materials. At the same time, after the mechanical stripping method is used to strip the prepared two-dimensional layered rare earth materials to obtain a few-layer material, it shows excellent photoelectric properties and is expected to be used in the preparation of luminescence and photoelectric detection devices.
[0022] (2) The raw material cost of the present invention is low, the process operation is simple, and it meets environmental protection requirements. In addition, the obtained two-dimensional layered rare earth material has promising application prospects in light-emitting devices and photoelectric detection devices. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 ReSiTe is a two-dimensional layered semiconductor material. 3 Growth flow chart of
[0024] Figure 2 It is a two-dimensional layered semiconductor material TmSiTe 3 Optical photographs of bulk single crystals;
[0025] Figure 3 It is a two-dimensional layered semiconductor material TmSiTe 3 The crystal structure of
[0026] Figure 4 It is a two-dimensional layered semiconductor material TmSiTe 3 XRD pattern of
[0027] Figure 5 It is a two-dimensional layered semiconductor material TmSiTe 3 EDS spectrum and atomic ratio;
[0028] Figure 6 It is a two-dimensional layered semiconductor material TmSiTe 3 Raman spectra;
[0029] Figure 7 It is a two-dimensional layered semiconductor material TmSiTe 3 The luminescence spectrum of
[0030] Figure 8 YSiTe is a two-dimensional layered semiconductor material. 3 Optical photographs of bulk single crystals;
[0031] Fig. 9 YSiTe is a two-dimensional layered semiconductor material. 3 The crystal structure of
[0032] Fig.10 YSiTe is a two-dimensional layered semiconductor material. 3 XRD pattern of
[0033] Fig.11 YSiTe is a two-dimensional layered semiconductor material. 3 Raman spectra;
[0034] Fig.12 HoSiTe is a two-dimensional layered semiconductor material. 3 Optical photographs of bulk single crystals;
[0035] Fig.13 HoSiTe is a two-dimensional layered semiconductor material. 3 The crystal structure of
[0036] Fig.14 HoSiTe is a two-dimensional layered semiconductor material. 3 XRD pattern of
[0037] Fig.15 HoSiTe is a two-dimensional layered semiconductor material. 3 Raman spectra;
[0038] Fig.16 For few-layer TmSiTe 3 Optical images of
[0039] Fig.17 It is a two-dimensional layered semiconductor material TmSiTe 3 Absorption spectrum and optical band gap;
[0040] Fig.18 It is a two-dimensional layered semiconductor material TmSiTe 3 Optical images of photodetector devices;
[0041] Fig.19 It is a two-dimensional layered semiconductor material TmSiTe 3 Optical response performance. DETAILED DESCRIPTION
[0042] The specific embodiments of the present invention are further described below. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention. In addition, the technical features involved in each embodiment of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0043] The experimental methods in the following examples are conventional methods unless otherwise specified, and the experimental materials used in the following examples are commercially available unless otherwise specified.
[0044] like Figure 1As shown in the process flow diagram, the present invention provides a method for preparing a two-dimensional layered rare earth material. The specific process is as follows: prepare a tube furnace, weigh rare earth metals (RE = Y, Ho, Lu, Tm), Si, Te powders and a transfer agent and place them in a quartz tube, and use a molecular pump to evacuate the vacuum to a vacuum degree of 1×10 -3 Pa, and then use a tube sealing machine to seal the quartz tube, put it into a dual-temperature zone tube furnace, heat the reaction end to 900°C in the first stage, heat the generation end to 1000°C, and cool the generation end to 850°C in the second stage. Both stages are subjected to constant temperature reactions according to the preset time, and the two-dimensional layered rare earth material is obtained by naturally cooling after the end. Among them, the molar ratio of the growth raw material RE:Si:Te is 1:1:3, and the total mass is 2-2.5g; the mass ratio of the total amount of the growth raw material to the amount of the transmission agent is 20:1; the transmission agent is I 2 .
[0045] The process flow for preparing two-dimensional layered rare earth materials and their excellent photoelectric properties are further described in detail below in conjunction with Examples 1-4.
[0046] Example 1
[0047] This embodiment provides a two-dimensional layered rare earth material TmSiTe 3 The preparation process is as follows:
[0048] (1) 2 g of raw material Tm, Si, Te powder (molar ratio of 1:1:3) and 0.1 g of transmission agent I 2 Place it in a quartz tube and evacuate it to a vacuum degree of 1×10 -3 After Pa, the quartz tube was sealed and placed in a dual-temperature zone tube furnace. The sintering temperature was set to 900°C at the reaction end, with a heating rate of 5°C / min; the generation end was 1000°C, with a heating rate of 10°C / min, and a holding time of 6h. A gaseous mixture was obtained after the reaction.
[0049] (2) The temperature of the generation end is reduced to 850°C, and the cooling rate is 10°C / min, and then the second sintering stage is entered. The temperature of the second sintering stage is 900°C at the reaction end and 850°C at the generation end, and the temperature is kept for 168 hours. After the reaction is completed, the temperature is naturally cooled to obtain a large-sized, high-quality two-dimensional rare earth compound TmSiTe 3 .
[0050] Figure 2 The TmSiTe prepared in Example 1 3 Optical photograph of a bulk single crystal with lateral dimensions exceeding 5 mm. Figure 3 The TmSiTe prepared in Example 1 3The crystal structure diagram has a space group of P(-1), unit cell parameters of a=7.3001(11), b=7.3058(7), c=7.8487(14), α=90.947°(11), β=116.918°(16), γ=116.095°(13). Figure 4 The TmSiTe prepared in Example 1 3 XRD spectrum of the generated TmSiTe 3 The in-plane crystal orientation is <001> surface, and there is no impurity phase, which is pure TmSiTe 3 Crystal. Figure 5 The TmSiTe prepared in Example 1 3 EDS spectrum of TmSiTe 3 Successfully prepared, the atomic ratio of Tm:Si:Te is 1:1:3. Figure 6 The TmSiTe prepared in Example 1 3 Raman spectrum of TmSiTe 3 Good crystallinity, Raman peak at 68cm -1 , 79cm -1 , 95cm -1 , 113cm -1 , 124cm -1 , 144cm -1 . Figure 7 The TmSiTe prepared in Example 1 3 From the fluorescence spectrum, we can see that TmSiTe 3 Red emission is obtained under 532 nm excitation.
[0051] Example 2
[0052] This embodiment provides a two-dimensional layered rare earth material YSiTe 3 The preparation process is as follows:
[0053] (1) 2 g of raw material Y, Si, Te powder (molar ratio of 1:1:3) and 0.1 g of transfer agent I 2 Place it in a quartz tube and evacuate it to a vacuum degree of 1×10 -3 After Pa, the quartz tube was sealed and placed in a dual-temperature zone tube furnace. The sintering temperature was set to 900°C at the reaction end, with a heating rate of 5°C / min; the generation end was 1000°C, with a heating rate of 10°C / min, and a holding time of 6h. A gaseous mixture was obtained after the reaction.
[0054] (2) The temperature of the generation end is reduced to 850°C, and the cooling rate is 10°C / min, and then the second sintering stage is entered. The temperature of the second sintering stage is 900°C at the reaction end and 850°C at the generation end, and the temperature is kept for 168 hours. After the reaction is completed, the large-sized, high-quality two-dimensional rare earth compound YSiTe is obtained by naturally cooling. 3 .
[0055] Figure 8 YSiTe prepared in Example 2 3 Optical photograph of a bulk single crystal. Fig. 9 YSiTe is a two-dimensional layered semiconductor material. 3 The crystal structure has a space group of C2 / m, unit cell parameters of a=7.804(2), b=4.1758(12), c=6.800(3), α=90°, β=93.19(3)°, γ=90°. Fig.10 YSiTe is a two-dimensional layered semiconductor material. 3 The XRD spectrum of the generated YSiTe 3 The crystal has no impurities and is pure YSiTe 3 Crystal. Fig.11 YSiTe is a two-dimensional layered semiconductor material. 3 From the Raman spectrum, we can see that YSiTe 3 Good crystallinity.
[0056] Example 3
[0057] This embodiment provides a two-dimensional layered rare earth material HoSiTe 3 The preparation process is as follows:
[0058] (1) 2 g of raw materials Ho, Si, Te powder (molar ratio of 1:1:3) and 0.1 g of transfer agent I 2 Place it in a quartz tube and evacuate it to a vacuum degree of 1×10 -3 After Pa, the quartz tube was sealed and placed in a dual-temperature zone tube furnace. The sintering temperature was set to 900°C at the reaction end, with a heating rate of 5°C / min; the generation end was 1000°C, with a heating rate of 10°C / min, and a holding time of 6h. A gaseous mixture was obtained after the reaction.
[0059] (2) The temperature of the generation end is reduced to 850°C at a cooling rate of 10°C / min, and then the second sintering stage is entered. The temperature of the second sintering stage is 900°C at the reaction end and 850°C at the generation end, and the temperature is kept for 168 hours. After the reaction is completed, the large-sized, high-quality two-dimensional rare earth compound HoSiTe is obtained by naturally cooling. 3 .
[0060] Fig.12The two-dimensional layered semiconductor material HoSiTe prepared in Example 3 3 Optical photographs of bulk single crystals; Fig.13 HoSiTe is a two-dimensional layered semiconductor material. 3 The crystal structure, space group is P(-1), unit cell parameters are a=7.3229(7), b=7.3443(8), c=7.8497(9), α=91.087°(9), β=116.918°(16), γ=116.115°(10); Fig.14 HoSiTe is a two-dimensional layered semiconductor material. 3 The XRD spectrum of the generated HoSiTe 3 The crystal has no impurities and is pure HoSiTe 3 Crystal. Fig.15 HoSiTe is a two-dimensional layered semiconductor material. 3 From the Raman spectrum, we can see that HoSiTe 3 Good crystallinity.
[0061] Example 4
[0062] (1) The obtained two-dimensional layered rare earth material (TmSiTe) was attached by Scotch tape. 3 ) is peeled off into a few layers of two-dimensional material by mechanical exfoliation, with a thickness of less than 100 nm, and transferred to a silicon wafer (the surface layer of the silicon wafer is silicon dioxide, silicon dioxide (SiO 2 ) thickness is 285nm).
[0063] (2) After the two-dimensional layered rare earth material is transferred to the silicon wafer, a layer of positive photoresist is spin-coated on the surface of the silicon wafer and heated on a heating table at 100°C for 4 minutes to fix and stabilize the positive photoresist;
[0064] (3) The positive photoresist in the specific electrode pattern area is modified by ultraviolet exposure using a photolithography machine, and the silicon wafer is then placed in a tetramethylammonium hydroxide solution as a developer for 10 seconds. After the development is completed, the wafer is taken out to obtain a blank area in the specific electrode pattern.
[0065] (4) 10 nm of Ti and 70 nm of Au are deposited on the surface of a silicon wafer by electron beam evaporation to obtain a conductive electrode. After the evaporation is completed, the silicon wafer is placed in an acetone solution to remove the unexposed positive photoresist and the metal on it, and finally the desired photodetector device is obtained.
[0066] Fig.16 TmSiTe prepared in Example 4 3 Optical photos of few-layer materials. From the optical photos, we can see that materials of different thicknesses show different colors, showing semiconductor properties.
[0067] Fig.17 TmSiTe prepared in Example 4 3 Absorption spectrum of the few-layer material, with an optical band gap of 1.49 eV.
[0068] Fig.18 TmSiTe prepared in Example 4 3 Photodetector devices. Fig.19 TmSiTe prepared in Example 4 3 The photoelectric response of the photodetector device under 671nm laser excitation. The test results show that the device has a significant photoelectric response, and the photoresponse increases with the increase of light intensity. The above photoelectric performance characterization confirms that the two-dimensional rare earth compound TmSiTe 3 There is an obvious photoelectric response, and it is expected to be used to prepare highly sensitive and fast-response two-dimensional rare earth compound multifunctional photoelectric detection devices, providing advanced solutions for fields such as photoelectric detection.
[0069] Similarly, using YSiTe 3 or HoSiTe 3 The fabricated photodetector device also has an obvious photoelectric response, and the photoresponse increases with the increase of light intensity. It is expected to be used to prepare highly sensitive and fast-response two-dimensional rare earth compound multifunctional photodetector devices.
[0070] The embodiments of the present invention are described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions and variations of these embodiments are made without departing from the principles and spirit of the present invention, and still fall within the protection scope of the present invention.
Claims
1. A new type of two-dimensional layered rare earth semiconductor material, characterized in that: The two-dimensional layered rare earth materials include YSiTe3, HoSiTe3, LuSiTe3, and TmSiTe3.
2. The novel two-dimensional layered rare earth semiconductor material according to claim 1, characterized in that: The lateral dimension of the two-dimensional layered rare earth material exceeds 5 mm.
3. The method for preparing the novel two-dimensional layered rare earth semiconductor material according to claim 1 or 2, characterized in that: The growth raw materials of rare earth metal RE (RE = Y, Ho, Lu, Tm), Si, Te powder and transfer agent are placed in a quartz tube, which is sealed after vacuuming, and then placed in a double-temperature zone tubular furnace for two-stage sintering treatment. In the first sintering stage, the raw materials are melted at the reaction end to form gaseous compounds. In the second sintering stage, the temperature of the generation end is changed. Under the action of the temperature gradient driving force, the gaseous compounds are transferred from the reaction end to the generation end, and physical vapor deposition is completed in this stage. After the end, the temperature is naturally lowered to obtain a two-dimensional layered rare earth material.
4. The method for preparing the novel two-dimensional layered rare earth semiconductor material according to claim 3, characterized in that: The molar ratio of the growth raw materials is RE:Si:Te=1:1:
3.
5. The method for preparing the novel two-dimensional layered rare earth semiconductor material according to claim 3, characterized in that: The mass ratio of the total amount of growth raw materials to the amount of transfer agent used is 20:1; the transfer agent is I2.
6. The method for preparing the novel two-dimensional layered rare earth semiconductor material according to claim 3, characterized in that: The temperature of the first sintering stage is 900°C at the reaction end, with a heating rate of 5°C / min; 1000°C at the generation end, with a heating rate of 10°C / min; and the temperature is kept for 6 hours.
7. The method for preparing the novel two-dimensional layered rare earth semiconductor material according to claim 3, characterized in that: The temperature of the second sintering stage is 900° C. at the reaction end and 850° C. at the production end, and the cooling rate at the production end is 10° C. / min; the temperature is kept for 168 hours.
8. Use of the novel two-dimensional layered rare earth semiconductor material according to claim 1 or 2 in light-emitting devices and / or photoelectric detection devices.
9. The use according to claim 8, characterized in that: First, the novel two-dimensional layered rare earth semiconductor material described in claim 1 or 2 is peeled off into a few-layer two-dimensional material by mechanical peeling method, and transferred to a silicon wafer by PDMS, and then a conductive electrode is prepared on the surface of the silicon wafer material by photolithography and electron beam evaporation process, so as to obtain a light-emitting device and / or a photoelectric detection device.
10. The use according to claim 9, characterized in that: The thickness of the few-layer two-dimensional material is less than 100 nm, and the conductive electrode is composed of 10 nm Ti and 70 nm Au.